WO2011080972A1 - Organic electroluminescent element - Google Patents

Organic electroluminescent element Download PDF

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WO2011080972A1
WO2011080972A1 PCT/JP2010/070536 JP2010070536W WO2011080972A1 WO 2011080972 A1 WO2011080972 A1 WO 2011080972A1 JP 2010070536 W JP2010070536 W JP 2010070536W WO 2011080972 A1 WO2011080972 A1 WO 2011080972A1
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organic
carbon atoms
layer
indolocarbazole
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PCT/JP2010/070536
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French (fr)
Japanese (ja)
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孝弘 甲斐
敏浩 山本
正樹 古森
めぐみ 松本
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新日鐵化学株式会社
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Priority to JP2011547407A priority Critical patent/JP5596706B2/en
Priority to US13/512,883 priority patent/US9260433B2/en
Priority to EP10840831.1A priority patent/EP2521196B1/en
Priority to KR1020127019438A priority patent/KR101758865B1/en
Priority to CN201080059524.8A priority patent/CN102696126B/en
Publication of WO2011080972A1 publication Critical patent/WO2011080972A1/en

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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1018—Heterocyclic compounds
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1018—Heterocyclic compounds
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    • C09K2211/1025—Heterocyclic compounds characterised by ligands
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission

Definitions

  • the present invention relates to an organic electroluminescent device containing an indolocarbazole compound, and more particularly to a thin film device that emits light by applying an electric field to a light emitting layer made of an organic compound.
  • an organic electroluminescence element (hereinafter referred to as an organic EL element) has a light emitting layer and a pair of counter electrodes sandwiching the layer as its simplest structure. That is, in an organic EL element, when an electric field is applied between both electrodes, electrons are injected from the cathode, holes are injected from the anode, and these are recombined in the light emitting layer to emit light. .
  • CBP 4,4′-bis (9-carbazolyl) biphenyl
  • Ir (ppy) 3 a green phosphorescent material typified by tris (2-phenylpyridine) iridium complex
  • CBP has a characteristic that it is easy to flow holes and electrons. The charge injection balance is lost, and excess holes flow out to the electron transport layer side. As a result, the light emission efficiency from Ir (ppy) 3 decreases.
  • a host material having high triplet excitation energy and balanced in both charge (hole / electron) injection and transport characteristics is required. Further, a compound that is electrochemically stable and has high heat resistance and excellent amorphous stability is desired, and further improvement is required.
  • Patent Document 3 an indolocarbazole compound as shown below is disclosed as a hole transport material.
  • Patent Document 4 an indolocarbazole compound as shown below is disclosed as a hole transport material.
  • Patent Document 5 discloses an indolocarbazole compound as shown below as a host material, and discloses that an organic EL device using the compound improves luminous efficiency and has high driving stability.
  • An object of this invention is to provide the practically useful organic EL element which has high efficiency and high drive stability in view of the said present condition, and a compound suitable for it.
  • the present invention relates to an organic electroluminescence device in which an anode, an organic layer including a phosphorescent light emitting layer and a cathode are laminated on a substrate, and a group consisting of a phosphorescent light emitting layer, a hole transport layer, an electron transport layer and a hole blocking layer.
  • An organic electroluminescent element comprising an indolocarbazole compound represented by the general formula (1) in at least one organic layer selected from:
  • L represents an (m + n + p + q) -valent aromatic hydrocarbon group having 6 to 50 carbon atoms or an (m + n + p + q) -valent aromatic heterocyclic group having 3 to 50 carbon atoms, Y 1 to Y
  • Each 4 is represented by any one of formulas (1a-1) to (1a-6), and at least one is a different group.
  • m is an integer of 1 to 3
  • n is an integer of 1 to 3
  • p is an integer of 0 to 3
  • q is an integer of 0 to 3
  • m + n + p + q is 2 to 6.
  • A is independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 11 carbon atoms, an aromatic hydrocarbon group having 6 to 50 carbon atoms, or carbon.
  • An aromatic heterocyclic group having a number of 3 to 50 is shown.
  • R 1 to R 3 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 11 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic group having 3 to 11 carbon atoms. Represents a heterocyclic group.
  • R 3 may form a condensed ring together with the six-membered ring which R 3 is attached.
  • indolocarbazole compounds represented by general formula (1) indolocarbazole compounds represented by the following general formulas (2) to (7) are more preferred compounds.
  • L, A, R 1 to R 3 , m and n are the same as the general formula (1) and the formulas (1a-1) to (1a-6).
  • m and n are more preferably 1.
  • the organic electroluminescent element preferably has a light emitting layer containing the indolocarbazole compound and a phosphorescent dopant.
  • the indolocarbazole compound used in the organic electroluminescence device of the present invention is an indolocarbazole compound represented by the general formula (1).
  • L is an aromatic hydrocarbon group having 6 to 50 carbon atoms or an aromatic heterocyclic group having 3 to 50 carbon atoms, and is an (m + n + p + q) valent group.
  • Y 1 to Y 4 are groups represented by any of the different formulas (1a-1) to (1a-6).
  • m is an integer of 1 to 3
  • n is an integer of 1 to 3
  • p is an integer of 0 to 3
  • q is an integer of 0 to 3
  • m + n + p + q is 2 to 6.
  • Y 1 to Y 4 are monovalent groups in which R 1 to R 3 and A are substituted on the indolocarbazole skeleton, and a linking group bonded to L is generated from the N atom in the indolocarbazole skeleton.
  • the indolocarbazole skeleton is formed by condensing five rings, but there are isomers having different condensation positions.
  • Y 1 to Y 4 are groups represented by the formulas (1a-1) to (1a-6), and Y 1 to Y 4 are different groups. At least two of Y 1 to Y 4 are present as different groups.
  • L represents an aromatic hydrocarbon group having 6 to 50 carbon atoms and an aromatic heterocyclic group having 3 to 50 carbon atoms.
  • L include benzene, naphthalene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, chrysene, pyridine, pyrimidine, triazine, quinoline, isoquinoline, quinoxaline, naphthyridine, carbazole, acridine, or an aromatic group in which a plurality of these aromatic rings are connected.
  • benzene, pyridine, pyrimidine, triazine, naphthalene, carbazole, or an (m + n + p + q) -valent group generated by removing hydrogen from an aromatic compound in which a plurality of these aromatic rings are connected is used.
  • a plurality of the aromatic rings are connected, they may be the same or different.
  • the group generated by removing hydrogen from the aromatic compound in which a plurality of aromatic rings are connected include, for example, biphenyl, terphenyl, bipyridine, bipyrimidine, vitriazine, bistriazylbenzene, binaphthalene, phenylpyridine, diphenylpyridine, diphenylpyrimidine , Diphenyltriazine, phenylcarbazole, pyridylcarbazole and the like (m + n + p + q) -valent groups are included, and the connecting position of Y 1 , Y 2 , Y 3 and Y 4 is not limited, and even in the terminal ring, the central part
  • the ring may be
  • the aromatic hydrocarbon group or aromatic heterocyclic group may have a substituent, and when it has a substituent, preferred substituents include an alkyl group having 1 to 4 carbon atoms and a group having 3 to 6 carbon atoms.
  • a group generated from an aromatic compound in which a plurality of aromatic rings are linked is a divalent group, for example, represented by the following formulas (11) to (13).
  • Ar 1 to Ar 6 each represents an unsubstituted monocyclic or condensed aromatic ring.
  • the total number of substituents is 1 to 10. Preferably it is 1-6, more preferably 1-4. Further, when L, A and R 1 to R 3 have two or more substituents, they may be the same or different. In addition, in the calculation of the carbon number of L, A and R 1 to R 3 , when it has a substituent, the carbon number of the substituent is included.
  • Y 1 to Y 4 are represented by the formulas (1a-1) to (1a-6), respectively.
  • R 1 , R 2 and R 3 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 11 carbon atoms, Represents a 6-12 aromatic hydrocarbon group or a C3-C11 aromatic heterocyclic group.
  • Preferred are hydrogen, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a naphthyl group, a carbazolyl group, a quinolyl group, and an isoquinolyl group.
  • they are hydrogen, a phenyl group, or a carbazolyl group.
  • R 3 forms a condensed ring with the central six-membered ring forming the indolocarbazole skeleton. May be.
  • R 3 may be a condensed ring.
  • an indole ring is preferable, and in this case, diindolocarbazole is formed. At this time, the indole ring may have a substituent.
  • the ring obtained by removing the six-membered ring from the condensed ring formed by condensation includes a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, It can be a thiophene ring, a benzene ring, a naphthalene ring or the like. These rings may have a substituent, and are preferably indole rings which may have a substituent. In this case, when the 6-membered ring is included, a carbazole ring may be formed. If R 3 is condensed with the six-membered ring is a case where R 3 has a substitutable hydrogen atoms of the adjacent position is substituted position on the six-membered ring.
  • A is independently a monovalent alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 11 carbon atoms, an aromatic hydrocarbon group having 6 to 50 carbon atoms, or an aromatic heterocyclic group having 3 to 50 carbon atoms. Show. Specific examples of preferred A include benzene, naphthalene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, chrysene, pyridine, pyrimidine, triazine, quinoline, isoquinoline, quinoxaline, naphthyridine, carbazole, acridine, or aromatics in which a plurality of these are linked.
  • a monovalent group generated by removing hydrogen from a compound can be mentioned. More preferably, a monovalent group produced by removing hydrogen from benzene, pyridine, pyrimidine, triazine, naphthalene, carbazole or an aromatic compound in which a plurality of these are linked is used. When a plurality of the aromatic compounds are connected, they may be the same or different.
  • Specific examples of the group generated by removing hydrogen from the above-described aromatic compounds linked together include, for example, biphenyl, terphenyl, bipyridine, bipyrimidine, bitriazine, bistriazylbenzene, phenylpyridine, diphenylpyridine, diphenylpyrimidine, diphenyltriazine, phenyl And monovalent groups derived from carbazole, pyridylcarbazole and the like.
  • the alkyl group, cycloalkyl group, aromatic hydrocarbon group or aromatic heterocyclic group may have a substituent, and when it has a substituent, preferred substituents include alkyl groups having 1 to 4 carbon atoms, An alkoxy group having 1 to 2 carbon atoms, an acetyl group, an aryl group having 6 to 18 carbon atoms, and a heteroaryl group having 3 to 17 carbon atoms. More preferred are a phenyl group, a naphthyl group, a carbazolyl group, a quinolyl group, and an isoquinolyl group. Further, the substitution position of A with N in the formulas (1a-1) to (1a-6) is not limited.
  • n represents an integer of 1 to 3.
  • m is an integer from 1 to 2, and more preferably, m is 1.
  • n represents an integer of 1 to 3.
  • n is an integer from 1 to 2, more preferably n is 1.
  • p represents an integer of 0-3.
  • p is an integer from 0 to 2, more preferably, p is 0 or 1.
  • q represents an integer of 0-3.
  • q is an integer from 0 to 2, and more preferably q is 0 or 1.
  • the sum of m, n, p and q is an integer of 2-6. It is preferably 2 to 4, more preferably 2 or 3.
  • the indolocarbazole compounds represented by the general formula (1) are preferable compounds.
  • Indolocarbazole compounds represented by the general formulas (1) to (7) can be synthesized by selecting a raw material according to the structure of the target compound and using a known method.
  • Indolocarbazole compounds that give an indolocarbazole skeleton represented by the formula (1a-2) can be obtained by referring to the synthesis examples shown in Archiv der Pharmazie (Weinheim, Germany) 1987, 320 (3), p280-2. Can be synthesized by the following reaction formula.
  • indolocarbazole compounds that give an indolocarbazole skeleton represented by formula (1a-3) and formula (1a-4) are The Journal of Organic Chemistry, 2007,72 (15) 5886 and Tetrahedron, 1999, It can be synthesized by the following reaction formula with reference to the synthesis example shown in p.
  • indolocarbazole compound represented by the general formula (1) Specific examples of the indolocarbazole compound represented by the general formula (1) are shown below, but the indolocarbazole compound used in the organic electroluminescence device of the present invention is not limited thereto.
  • the indolocarbazole compound represented by the general formula (1) is excellent by being contained in at least one organic layer of an organic EL device in which an anode, a plurality of organic layers and a cathode are laminated on a substrate.
  • An organic electroluminescent device is provided.
  • a light emitting layer, a hole transport layer, an electron transport layer or a hole blocking layer is suitable. More preferably, it may be contained as a host material of a light emitting layer containing a phosphorescent dopant.
  • the organic EL device of the present invention has an organic layer having at least one light emitting layer between an anode and a cathode laminated on a substrate, and at least one organic layer contains the indolocarbazole compound.
  • the indolocarbazole compound is included in the light emitting layer together with a phosphorescent dopant.
  • the structure of the organic EL element of the present invention will be described with reference to the drawings.
  • the structure of the organic EL element of the present invention is not limited to the illustrated one.
  • FIG. 1 is a cross-sectional view showing a structural example of a general organic EL device used in the present invention, wherein 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, and 5 is a light emitting layer. , 6 represents an electron transport layer, and 7 represents a cathode.
  • the organic EL device of the present invention may have an exciton blocking layer adjacent to the light emitting layer, and may have an electron blocking layer between the light emitting layer and the hole injection layer.
  • the exciton blocking layer can be inserted on either the anode side or the cathode side of the light emitting layer, or both can be inserted simultaneously.
  • the organic EL device of the present invention has a substrate, an anode, a light emitting layer and a cathode as essential layers, but it is preferable to have a hole injecting and transporting layer and an electron injecting and transporting layer in layers other than the essential layers, and further emit light. It is preferable to have a hole blocking layer between the layer and the electron injecting and transporting layer.
  • the hole injection / transport layer means either or both of a hole injection layer and a hole transport layer
  • the electron injection / transport layer means either or both of an electron injection layer and an electron transport layer.
  • the organic EL element of the present invention is preferably supported on a substrate.
  • the substrate is not particularly limited as long as it is conventionally used for an organic EL element.
  • a substrate made of glass, transparent plastic, quartz, or the like can be used.
  • an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
  • electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 and ZnO.
  • conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) that can form a transparent conductive film may be used.
  • these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not required (about 100 ⁇ m or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. Or when using the substance which can be apply
  • the cathode a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
  • an electron injecting metal a material having a low work function (4 eV or less) metal
  • an alloy a material having a low work function (4 eV or less) metal
  • an alloy a material having a low work function (4 eV or less) metal
  • an alloy referred to as an electron injecting metal
  • an alloy referred to as an electron injecting metal
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this for example, a magnesium / silver mixture
  • Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum and the like.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the light emission luminance is improved, which is convenient.
  • a transparent or semi-transparent cathode can be produced by producing the conductive transparent material mentioned in the description of the anode on the cathode after producing the metal with a thickness of 1 to 20 nm on the cathode.
  • an element in which both the anode and the cathode are transmissive can be manufactured.
  • the light emitting layer is a phosphorescent light emitting layer and includes a phosphorescent dopant and a host material.
  • the phosphorescent dopant material preferably contains an organometallic complex containing at least one metal selected from ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum and gold. Such organometallic complexes are known in the prior art documents and the like, and these can be selected and used.
  • Preferable phosphorescent dopants include complexes such as Ir (ppy) 3 having a noble metal element such as Ir as a central metal, complexes such as (Bt) 2 Iracac, and complexes such as (Btp) Ptacac. Specific examples of these complexes are shown below, but are not limited to the following compounds.
  • the amount of the phosphorescent dopant contained in the light emitting layer is preferably in the range of 5 to 30% by weight.
  • the host material in the light emitting layer it is preferable to use an indolocarbazole compound represented by the general formula (1).
  • the material used for the light emitting layer may be a host material other than the indolocarbazole compound.
  • An indolocarbazole compound and another host material may be used in combination.
  • a plurality of known host materials may be used in combination.
  • a known host compound that can be used is preferably a compound that has a hole transporting ability and an electron transporting ability, prevents a long wavelength of light emission, and has a high glass transition temperature.
  • host materials are known from a large number of patent documents and can be selected from them.
  • Specific examples of the host material are not particularly limited, but include indole derivatives, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine.
  • arylamine derivatives amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, anthraquino Heterocyclic tetracarboxylic acid anhydrides such as dimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene,
  • metal complexes typified by metal complexes of Russianine derivatives, 8-quinolinol derivatives, metal phthalocyanines, metal complexes of benzoxazole and benzothiazole derivatives, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline copolymers, Examples thereof include polymer compounds such
  • the injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of light emission.
  • the injection layer can be provided as necessary.
  • the hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking.
  • the indolocarbazole compound represented by the general formula (1) for the hole blocking layer.
  • a known hole blocking layer is used. Materials may be used.
  • a hole-blocking layer material the material of the electron carrying layer mentioned later can be used as needed.
  • the electron blocking layer is made of a material that has a function of transporting holes and has a very small ability to transport electrons.
  • the electron blocking layer blocks the electrons while transporting holes, and the probability of recombination of electrons and holes. Can be improved.
  • the indolocarbazole compound represented by the general formula (1) according to the present invention can be used.
  • the material for the hole transport layer described later is used as necessary. It can also be used.
  • the thickness of the electron blocking layer is preferably 3 to 100 nm, more preferably 5 to 30 nm.
  • the exciton blocking layer is a layer for preventing excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. It becomes possible to efficiently confine in the light emitting layer, and the light emission efficiency of the device can be improved.
  • the exciton blocking layer can be inserted on either the anode side or the cathode side adjacent to the light emitting layer, or both can be inserted simultaneously.
  • an indolocarbazole compound represented by the general formula (1) can be used as the material for the exciton blocking layer.
  • other materials for example, 1,3-dicarbazolylbenzene (mCP), Bis (2-methyl-8-quinolinolato) -4-phenylphenolato aluminum (III) (BAlq).
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport material has either hole injection or transport or electron barrier properties, and may be either organic or inorganic. Although it is preferable to use the indolocarbazole compound represented by General formula (1) for a positive hole transport layer, arbitrary things can be selected and used from a conventionally well-known compound.
  • Examples of known hole transport materials that can be used include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, Examples include styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. Porphyrin compounds, aromatic tertiary amine compounds, and styryl. It is preferable to use an amine compound, and it is more preferable to use an aromatic tertiary amine compound.
  • the electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer can be provided as a single layer or a plurality of layers.
  • an electron transport material (which may also serve as a hole blocking material), it is sufficient if it has a function of transmitting electrons injected from the cathode to the light emitting layer.
  • any one of conventionally known compounds can be selected and used. For example, nitro-substituted fluorene Derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • Concentrated hydrochloric acid 112.0 g (1.10 mol) was added dropwise over 21 hours to 211.7 g (2.16 mol) of concentrated sulfuric acid while stirring a solution of indium 20.0 g (0.17 mol) in 300 ml of dehydrated diethyl ether at room temperature in a nitrogen atmosphere. Injected hydrogen chloride gas. After stirring the reaction solution at room temperature for 15 hours, 121.0 g of ethyl acetate and 303.2 g of saturated aqueous sodium hydrogen carbonate solution were added.
  • the reaction solution was divided into an organic layer and an aqueous layer, and the organic layer was washed with distilled water (2 ⁇ 300 ml) and further washed once with a saturated saline solution, and then the organic layer was dehydrated with magnesium sulfate. After filtering off magnesium sulfate, the solvent was distilled off under reduced pressure. To the obtained viscous liquid, 1000 g of n-hexane was added, and the mixture was heated and stirred. Thereafter, hot filtration was performed to remove insoluble matters. The filtrate was cooled, and the precipitated needle crystals were collected by filtration and dried to obtain Intermediate D 73.3 g (0.32 mol, yield 75%).
  • Example 1 Each thin film was laminated at a vacuum degree of 4.0 ⁇ 10 ⁇ 5 Pa by a vacuum deposition method on a glass substrate on which an anode made of ITO having a thickness of 110 nm was formed.
  • copper phthalocyanine (CuPC) was formed to a thickness of 25 nm on ITO.
  • NPB 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • compound 3-15 obtained in Synthesis Example 1 as a host material, tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3 ) as a phosphorescent dopant, and Were co-deposited from different deposition sources to form a light emitting layer with a thickness of 40 nm.
  • the concentration of Ir (ppy) 3 in the light emitting layer was 10.0 wt%.
  • tris (8-hydroxyquinolinato) aluminum (III) (Alq3) was formed to a thickness of 20 nm as an electron transport layer.
  • lithium fluoride (LiF) was formed to a thickness of 1.0 nm as an electron injection layer.
  • aluminum (Al) was formed as an electrode to a thickness of 70 nm to produce an organic EL element.
  • the organic EL element had the light emission characteristics as shown in Table 1.
  • Table 1 the luminance, voltage, and luminous efficiency show values at 10 mA / cm 2 . Further, the luminance half time is evaluated by constant current drive of 40 mA / cm 2 , and the result is converted into a value when the initial luminance is 1000 cd / m 2 . The maximum wavelength of the device emission spectrum was 520 nm, and it was found that light emission from Ir (ppy) 3 was obtained.
  • Example 2 An organic EL device was produced in the same manner as in Example 1 except that Compound 1-31 was used as the host material for the light emitting layer.
  • Example 3 An organic EL device was produced in the same manner as in Example 1 except that Compound 2-3 was used as the host material for the light emitting layer.
  • Example 4 An organic EL device was produced in the same manner as in Example 1 except that Compound 3-22 was used as the host material for the light emitting layer.
  • Example 5 An organic EL device was produced in the same manner as in Example 1 except that Compound 5-19 was used as the host material for the light emitting layer.
  • Example 6 An organic EL device was produced in the same manner as in Example 1 except that Compound 6-11 was used as the host material for the light emitting layer.
  • Example 7 An organic EL device was produced in the same manner as in Example 1 except that Compound 6-17 was used as the host material for the light emitting layer.
  • Example 8 An organic EL device was produced in the same manner as in Example 1 except that Compound 6-30 was used as the host material for the light emitting layer.
  • Comparative Example 1 An organic EL device was produced in the same manner as in Example 1 except that the following compound H-1 was used as the host material for the light emitting layer.
  • the organic EL elements of Examples 1 to 8 have improved initial characteristics and lifetime characteristics as compared with Comparative Example 1. From this, a material having a different indolocarbazole skeleton in one molecule is used as a main component of the light emitting layer. This shows that the characteristics of the organic EL element are improved.
  • the indolocarbazole compound used in the organic electroluminescence device of the present invention has two or more types of indolocarbazole isomer skeleton in one molecule, or a bond having an asymmetric molecular structure even in the same isomer.
  • By having a mode it becomes possible to finely adjust the hole and electron transfer speeds and to control various energy values of IP, EA, and T1.
  • the optimum carrier balance in the light emitting layer is realized, and the effect characteristics can be greatly improved.
  • this indolocarbazole compound can improve stability in each active state of oxidation, reduction, and excitation, and at the same time has good amorphous characteristics, so it has a long driving life and high durability. An element can be realized.
  • a material design provided with functions such as improvement in solubility is possible, and a material more suitable for a wet process can be provided.
  • the organic EL device according to the present invention has practically satisfactory levels in terms of light emission characteristics, driving life and durability, flat panel display (mobile phone display device, in-vehicle display device, OA computer display device, television, etc.), surface light emission, etc. Its technical value is great in applications to light sources (lighting, light sources for copying machines, backlight light sources for liquid crystal displays and instruments), display boards, and sign lamps that make use of the characteristics of the body.

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Abstract

Disclosed is an organic electroluminescent element (organic EL element) which has a simple structure and improved luminous efficiency, while achieving sufficient operational stability. Specifically disclosed is an organic EL element comprising a light emitting layer between a positive electrode and a negative electrode that are arranged on a substrate, which is characterized in that the light emitting layer contains a phosphorescent dopant and an unsymmetrical indolocarbazole compound that serves as a host material. The unsymmetrical indolocarbazole compound has a structure wherein two or more groups having an indolocarbazole structure are connected by a linking group, and at least one group having an indolocarbazole structure is an isomer group that has a skeleton different from those of the other groups. Examples of the unsymmetrical indolocarbazole compound may include compounds represented by formula (2) wherein A represents a substituent, R1-R3 each represents a hydrogen atom or a substituent, and L represents a linking group that is composed of an aromatic group.

Description

有機電界発光素子Organic electroluminescence device
  本発明はインドロカルバゾール化合物を含有する有機電界発光素子に関するものであり、詳しくは、有機化合物からなる発光層に電界をかけて光を放出する薄膜型デバイスに関するものである。 The present invention relates to an organic electroluminescent device containing an indolocarbazole compound, and more particularly to a thin film device that emits light by applying an electric field to a light emitting layer made of an organic compound.
  一般に、有機電界発光素子（以下、有機ＥＬ素子という）は、その最も簡単な構造としては発光層及び該層を挟んだ一対の対向電極から構成されている。すなわち、有機ＥＬ素子では、両電極間に電界が印加されると、陰極から電子が注入され、陽極から正孔が注入され、これらが発光層において再結合し、光を放出する現象を利用する。 In general, an organic electroluminescence element (hereinafter referred to as an organic EL element) has a light emitting layer and a pair of counter electrodes sandwiching the layer as its simplest structure. That is, in an organic EL element, when an electric field is applied between both electrodes, electrons are injected from the cathode, holes are injected from the anode, and these are recombined in the light emitting layer to emit light. .
  近年、有機薄膜を用いた有機ＥＬ素子の開発が行われるようになった。特に、発光効率を高めるため、電極からキャリアー注入の効率向上を目的として電極の種類の最適化を行い、芳香族ジアミンからなる正孔輸送層と8-ヒドロキシキノリンアルミニウム錯体（以下、Alq3という）からなる発光層とを電極間に薄膜として設けた素子の開発により、従来のアントラセン等の単結晶を用いた素子と比較して大幅な発光効率の改善がなされたことから、自発光・高速応答性といった特徴を持つ高性能フラットパネルへの実用化を目指して進められてきた。 In recent years, organic EL elements using organic thin films have been developed. In particular, in order to increase luminous efficiency, the type of electrode was optimized for the purpose of improving the efficiency of carrier injection from the electrode. From the hole transport layer made of aromatic diamine and 8-hydroxyquinoline aluminum complex (hereinafter referred to as Alq3) As a result of the development of a device with a light emitting layer as a thin film between the electrodes, the luminous efficiency has been greatly improved compared to conventional devices using single crystals such as anthracene. It has been promoted with the aim of putting it into practical use for high-performance flat panels with these characteristics.
  また、素子の発光効率を上げる試みとして、蛍光ではなく燐光を用いることも検討されている。上記の芳香族ジアミンからなる正孔輸送層とAlq3からなる発光層とを設けた素子をはじめとした多くの素子が蛍光発光を利用したものであったが、燐光発光を用いる、すなわち、三重項励起状態からの発光を利用することにより、従来の蛍光（一重項）を用いた素子と比べて、３～４倍程度の効率向上が期待される。この目的のためにクマリン誘導体やベンゾフェノン誘導体を発光層とすることが検討されてきたが、極めて低い輝度しか得られなかった。また、三重項状態を利用する試みとして、ユーロピウム錯体を用いることが検討されてきたが、これも高効率の発光には至らなかった。近年では、特許文献１に挙げられるように発光の高効率化や長寿命化を目的にイリジウム錯体等の有機金属錯体を中心に燐光発光ドーパント材料の研究が多数行われている。 In addition, as an attempt to increase the luminous efficiency of the device, the use of phosphorescence instead of fluorescence has been studied. Many devices, including those provided with the hole transport layer composed of the above aromatic diamine and the light emitting layer composed of Alq3, used fluorescence emission, but use phosphorescence emission, that is, triplet. By using the light emitted from the excited state, the efficiency is expected to be improved by about 3 to 4 times compared to the conventional device using fluorescence (singlet). For this purpose, it has been studied to use a coumarin derivative or a benzophenone derivative as a light emitting layer, but only an extremely low luminance was obtained. In addition, as an attempt to use the triplet state, the use of a europium complex has been studied, but this also did not lead to highly efficient light emission. In recent years, as described in Patent Document 1, many studies on phosphorescent dopant materials have been conducted with a focus on organometallic complexes such as iridium complexes for the purpose of improving the efficiency of light emission and extending the lifetime.
特表2003-515897号公報Special Table 2003-515897 特開2001-313178号公報JP 2001-313178 A 特開平11-162650号公報Japanese Patent Laid-Open No. 11-162650 特開平11-176578号公報Japanese Patent Laid-Open No. 11-176578 WO2007-063754号公報WO2007-063754 Publication
  高い発光効率を得るには、前記ドーパント材料と同時に、使用するホスト材料が重要になる。ホスト材料として提案されている代表的なものとして、特許文献２で紹介されているカルバゾール化合物の4,4'-ビス(9-カルバゾリル)ビフェニル（以下、CBPという）が挙げられる。CBPはトリス(2-フェニルピリジン)イリジウム錯体（以下、Ir(ppy)3という）に代表される緑色燐光発光材料のホスト材料として使用した場合、CBPは正孔を流し易く電子を流しにくい特性上、電荷注入バランスが崩れ、過剰の正孔は電子輸送層側に流出し、結果としてIr(ppy)3からの発光効率が低下する。 In order to obtain high luminous efficiency, the host material to be used is important simultaneously with the dopant material. A representative example of a host material proposed is 4,4′-bis (9-carbazolyl) biphenyl (hereinafter referred to as CBP), which is a carbazole compound introduced in Patent Document 2. When CBP is used as a host material for a green phosphorescent material typified by tris (2-phenylpyridine) iridium complex (hereinafter referred to as Ir (ppy) 3 ), CBP has a characteristic that it is easy to flow holes and electrons. The charge injection balance is lost, and excess holes flow out to the electron transport layer side. As a result, the light emission efficiency from Ir (ppy) 3 decreases.
  前述のように、有機ＥＬ素子で高い発光効率を得るには、高い三重項励起エネルギーを有し、かつ両電荷（正孔・電子）注入輸送特性においてバランスがとれたホスト材料が必要である。更に、電気化学的に安定であり、高い耐熱性と共に優れたアモルファス安定性を備える化合物が望まれており、更なる改良が求められている。 As described above, in order to obtain high luminous efficiency in an organic EL element, a host material having high triplet excitation energy and balanced in both charge (hole / electron) injection and transport characteristics is required. Further, a compound that is electrochemically stable and has high heat resistance and excellent amorphous stability is desired, and further improvement is required.
  特許文献３においては、正孔輸送材料として以下に示すようなインドロカルバゾール化合物が開示されている。 In Patent Document 3, an indolocarbazole compound as shown below is disclosed as a hole transport material.

Figure JPOXMLDOC01-appb-I000004
 
Figure JPOXMLDOC01-appb-I000004
 
  特許文献４においては、正孔輸送材料として以下に示すようなインドロカルバゾール化合物が開示されている。

Figure JPOXMLDOC01-appb-I000005
  In Patent Document 4, an indolocarbazole compound as shown below is disclosed as a hole transport material.

Figure JPOXMLDOC01-appb-I000005
  しかしながら、これらはインドロカルバゾール骨格を有する化合物を正孔輸送材料としての使用を推奨するものの、蛍光発光素子においての実施例のみであり、燐光発光素子用材料としての使用を開示するものではない。 However, although it is recommended to use a compound having an indolocarbazole skeleton as a hole transport material, these are only examples in a fluorescent light emitting device, and do not disclose use as a material for a phosphorescent light emitting device.
  特許文献５にはホスト材料として以下に示すようなインドロカルバゾール化合物が開示され、これを使用した有機ＥＬ素子は発光効率を改善し、高い駆動安定性を有するものとなることを開示する。

Figure JPOXMLDOC01-appb-I000006
  Patent Document 5 discloses an indolocarbazole compound as shown below as a host material, and discloses that an organic EL device using the compound improves luminous efficiency and has high driving stability.

Figure JPOXMLDOC01-appb-I000006
  有機ＥＬ素子をフラットパネルディスプレイ等の表示素子に応用するためには、素子の発光効率を改善すると同時に駆動時の安定性を十分に確保する必要がある。本発明は、上記現状に鑑み、高効率かつ高い駆動安定性を有した実用上有用な有機ＥＬ素子及びそれに適する化合物を提供することを目的とする。 In order to apply the organic EL element to a display element such as a flat panel display, it is necessary to improve the light emission efficiency of the element and at the same time ensure the stability during driving. An object of this invention is to provide the practically useful organic EL element which has high efficiency and high drive stability in view of the said present condition, and a compound suitable for it.
  本発明者らは、鋭意検討した結果、特定構造のインドロカルバゾール骨格を有する化合物を有機ＥＬ素子として用いることで優れた特性を示すことを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that a compound having an indolocarbazole skeleton having a specific structure is used as an organic EL element, and have completed the present invention.
  本発明は、基板上に、陽極、燐光発光層を含む有機層及び陰極が積層されてなる有機電界発光素子において、燐光発光層、正孔輸送層、電子輸送層及び正孔阻止層からなる群れから選ばれる少なくとも一つの有機層中に、一般式（１）で表されるインドロカルバゾール化合物を含有することを特徴とする有機電界発光素子である。 The present invention relates to an organic electroluminescence device in which an anode, an organic layer including a phosphorescent light emitting layer and a cathode are laminated on a substrate, and a group consisting of a phosphorescent light emitting layer, a hole transport layer, an electron transport layer and a hole blocking layer. An organic electroluminescent element comprising an indolocarbazole compound represented by the general formula (1) in at least one organic layer selected from:
Figure JPOXMLDOC01-appb-I000007
 
Figure JPOXMLDOC01-appb-I000007
 
  一般式（１）中、Ｌは（ｍ＋ｎ＋ｐ＋ｑ）価の炭素数６～５０の芳香族炭化水素基、又は（ｍ＋ｎ＋ｐ＋ｑ）価の炭素数３～５０の芳香族複素環基を表し、Ｙ1～Ｙ4はそれぞれ式（1a-1）～（1a-6）のいずれかで表され、少なくとも1つは異なる基である。ｍは１～３の整数、ｎは１～３の整数、ｐは０～３の整数、ｑは０～３の整数を表し、ｍ＋ｎ＋ｐ＋ｑは２～６である。
Figure JPOXMLDOC01-appb-I000008
  In the general formula (1), L represents an (m + n + p + q) -valent aromatic hydrocarbon group having 6 to 50 carbon atoms or an (m + n + p + q) -valent aromatic heterocyclic group having 3 to 50 carbon atoms, Y 1 to Y Each 4 is represented by any one of formulas (1a-1) to (1a-6), and at least one is a different group. m is an integer of 1 to 3, n is an integer of 1 to 3, p is an integer of 0 to 3, q is an integer of 0 to 3, and m + n + p + q is 2 to 6.
Figure JPOXMLDOC01-appb-I000008
  式（1a-1）～（1a-6）中、Ａは独立に炭素数１～１０のアルキル基、炭素数３～１１のシクロアルキル基、炭素数６～５０の芳香族炭化水素基又は炭素数３～５０の芳香族複素環基を示す。Ｒ1～Ｒ3はそれぞれ独立に、水素、炭素数１～１０のアルキル基、炭素数３～１１のシクロアルキル基、炭素数６～１２の芳香族炭化水素基又は炭素数３～１１の芳香族複素環基を示す。ただし、（1a-1）、（1a-2）、（1a-4）及び（1a-6）において、Ｒ3はＲ3が結合する六員環と共に縮合環を形成しても良い。 In formulas (1a-1) to (1a-6), A is independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 11 carbon atoms, an aromatic hydrocarbon group having 6 to 50 carbon atoms, or carbon. An aromatic heterocyclic group having a number of 3 to 50 is shown. R 1 to R 3 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 11 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic group having 3 to 11 carbon atoms. Represents a heterocyclic group. However, (1a-1), ( 1a-2), in (1a-4) and (1a-6), R 3 may form a condensed ring together with the six-membered ring which R 3 is attached.
  一般式（１）で表されるインドロカルバゾール化合物の中でも、下記一般式（２）～（７）で表されるインドロカルバゾール化合物が、より好ましい化合物として挙げられる。 Among the indolocarbazole compounds represented by general formula (1), indolocarbazole compounds represented by the following general formulas (2) to (7) are more preferred compounds.

Figure JPOXMLDOC01-appb-I000009
 
Figure JPOXMLDOC01-appb-I000009
 
  一般式（２）～（７）中、Ｌ、Ａ、Ｒ1～Ｒ3、ｍ及びｎは一般式（１）及び式（1a-1）～（1a-6）と同意である。 In the general formulas (2) to (7), L, A, R 1 to R 3 , m and n are the same as the general formula (1) and the formulas (1a-1) to (1a-6).
  一般式（２）～（７）で表されるインドロカルバゾール化合物において、ｍ及びｎは１であることが更に好ましい。 In the indolocarbazole compounds represented by general formulas (2) to (7), m and n are more preferably 1.
  また、上記有機電界発光素子は上記インドロカルバゾール化合物と燐光発光ドーパントを含有する発光層を有することが好ましい。 In addition, the organic electroluminescent element preferably has a light emitting layer containing the indolocarbazole compound and a phosphorescent dopant.
有機ＥＬ素子の一構造例を示す断面図である。It is sectional drawing which shows one structural example of an organic EL element. 化合物3-15の1Ｈ－ＮＭＲチャートを示す。 1 H-NMR chart of Compound 3-15 is shown.
  本発明の有機電界発光素子において使用されるインドロカルバゾール化合物は、前記一般式（１）で表されるインドロカルバゾール化合物である。一般式（１）中、Ｌは炭素数６～５０の芳香族炭化水素基又は炭素数３～５０の芳香族複素環基であり、（ｍ＋ｎ＋ｐ＋ｑ）価の基である。Ｙ1～Ｙ4はそれぞれ異なる式（1a-1）～（1a-6）のいずれかで表される基である。ｍは１～３の整数、ｎは１～３の整数、ｐは０～３の整数、ｑは０～３の整数を表し、ｍ＋ｎ＋ｐ＋ｑは２～６である。 The indolocarbazole compound used in the organic electroluminescence device of the present invention is an indolocarbazole compound represented by the general formula (1). In the general formula (1), L is an aromatic hydrocarbon group having 6 to 50 carbon atoms or an aromatic heterocyclic group having 3 to 50 carbon atoms, and is an (m + n + p + q) valent group. Y 1 to Y 4 are groups represented by any of the different formulas (1a-1) to (1a-6). m is an integer of 1 to 3, n is an integer of 1 to 3, p is an integer of 0 to 3, q is an integer of 0 to 3, and m + n + p + q is 2 to 6.
  Ｙ1～Ｙ4は、インドロカルバゾール骨格にＲ1～Ｒ3、及びＡが置換し、インドロカルバゾール骨格中のＮ原子からＬと結合する結合基が生じている１価の基である。インドロカルバゾール骨格は、５つの環が縮合して生じているが、その縮合位置が相違する異性体が存在する。Ｙ1～Ｙ4は、式（1a-1）～（1a-6）で表される基であり、Ｙ1～Ｙ4は異なる基である。Ｙ1～Ｙ4の内、少なくとも２つは相互に異なる基として存在する。２つ以上の異なるインドロカルバゾール異性体骨格を特定の連結基で結合した構造、又は同一異性体であっても分子構造が非対称となる結合様式を有することにより、上記のような優れた効果をもたらすと考えられる。 Y 1 to Y 4 are monovalent groups in which R 1 to R 3 and A are substituted on the indolocarbazole skeleton, and a linking group bonded to L is generated from the N atom in the indolocarbazole skeleton. The indolocarbazole skeleton is formed by condensing five rings, but there are isomers having different condensation positions. Y 1 to Y 4 are groups represented by the formulas (1a-1) to (1a-6), and Y 1 to Y 4 are different groups. At least two of Y 1 to Y 4 are present as different groups. By having a structure in which two or more different indolocarbazole isomer skeletons are bonded by a specific linking group, or a bonding mode in which the molecular structure is asymmetric even in the same isomer, the above excellent effects can be obtained. It is thought to bring.
  一般式（１）において、Ｌは炭素数６～５０の芳香族炭化水素基、炭素数３～５０の芳香族複素環基を表す。Ｌの具体例としてはベンゼン、ナフタレン、フルオレン、アントラセン、フェナントレン、フルオランテン、ピレン、クリセン、ピリジン、ピリミジン、トリアジン、キノリン、イソキノリン、キノキサリン、ナフチリジン、カルバゾール、アクリジン又はこれら芳香環が複数連結された芳香族化合物から（ｍ＋ｎ＋ｐ＋ｑ）個の水素を除いて生じる（ｍ＋ｎ＋ｐ＋ｑ）価の基が挙げられる。好ましくは、ベンゼン、ピリジン、ピリミジン、トリアジン、ナフタレン、カルバゾール又はこれら芳香環が複数連結された芳香族化合物から水素を除いて生じる（ｍ＋ｎ＋ｐ＋ｑ）価の基が挙げられる。上記芳香環が複数連結される場合、それらは同一でも異なっていてもよい。上記芳香環が複数連結された芳香族化合物から水素を除いて生じる基の具体例としては、例えばビフェニル、ターフェニル、ビピリジン、ビピリミジン、ビトリアジン、ビストリアジルベンゼン、ビナフタレン、フェニルピリジン、ジフェニルピリジン、ジフェニルピリミジン、ジフェニルトリアジン、フェニルカルバゾール、ピリジルカルバゾール等から生じる（ｍ＋ｎ＋ｐ＋ｑ）価の基が挙げられ、Ｙ1、Ｙ2、Ｙ3及びＹ4の連結位置は限定されず、末端の環であっても中央部の環であっても構わない。上記芳香族炭化水素基又は芳香族複素環基は、置換基を有してもよく、置換基を有する場合、好ましい置換基としては、炭素数１～４のアルキル基、炭素数３～６のシクロアルキル基、炭素数１～２のアルコキシ基、アセチル基又は炭素数６～２４のジアリールアミノ基である。 In the general formula (1), L represents an aromatic hydrocarbon group having 6 to 50 carbon atoms and an aromatic heterocyclic group having 3 to 50 carbon atoms. Specific examples of L include benzene, naphthalene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, chrysene, pyridine, pyrimidine, triazine, quinoline, isoquinoline, quinoxaline, naphthyridine, carbazole, acridine, or an aromatic group in which a plurality of these aromatic rings are connected. (M + n + p + q) -valent group generated by removing (m + n + p + q) hydrogen atoms from the compound. Preferably, benzene, pyridine, pyrimidine, triazine, naphthalene, carbazole, or an (m + n + p + q) -valent group generated by removing hydrogen from an aromatic compound in which a plurality of these aromatic rings are connected is used. When a plurality of the aromatic rings are connected, they may be the same or different. Specific examples of the group generated by removing hydrogen from the aromatic compound in which a plurality of aromatic rings are connected include, for example, biphenyl, terphenyl, bipyridine, bipyrimidine, vitriazine, bistriazylbenzene, binaphthalene, phenylpyridine, diphenylpyridine, diphenylpyrimidine , Diphenyltriazine, phenylcarbazole, pyridylcarbazole and the like (m + n + p + q) -valent groups are included, and the connecting position of Y 1 , Y 2 , Y 3 and Y 4 is not limited, and even in the terminal ring, the central part The ring may be The aromatic hydrocarbon group or aromatic heterocyclic group may have a substituent, and when it has a substituent, preferred substituents include an alkyl group having 1 to 4 carbon atoms and a group having 3 to 6 carbon atoms. A cycloalkyl group, an alkoxy group having 1 to 2 carbon atoms, an acetyl group, or a diarylamino group having 6 to 24 carbon atoms.
  ここで、芳香環が複数連結された芳香族化合物から生じる基は、２価の基の場合、例えば、下記式（１１）～（１３）で表わされる。 基 Here, a group generated from an aromatic compound in which a plurality of aromatic rings are linked is a divalent group, for example, represented by the following formulas (11) to (13).
　　
Figure JPOXMLDOC01-appb-I000010
 
（式（１１）～（１３）中、Ａｒ1～Ａｒ6は無置換の単環又は縮合環の芳香環を表す。）
Figure JPOXMLDOC01-appb-I000010

(In the formulas (11) to (13), Ar 1 to Ar 6 each represents an unsubstituted monocyclic or condensed aromatic ring.)
  Ｌ、Ａ及びＲ1～Ｒ3が置換基を有する場合、置換基の総数は１～１０である。好ましくは１～６であり、より好ましくは１～４である。また、Ｌ、Ａ及びＲ1～Ｒ3が２つ以上の置換基を有する場合、それらは同一でも異なっていてもよい。また、Ｌ、Ａ及びＲ1～Ｒ3の炭素数の計算において、置換基を有する場合、その置換基の炭素数を含む。 When L, A and R 1 to R 3 have a substituent, the total number of substituents is 1 to 10. Preferably it is 1-6, more preferably 1-4. Further, when L, A and R 1 to R 3 have two or more substituents, they may be the same or different. In addition, in the calculation of the carbon number of L, A and R 1 to R 3 , when it has a substituent, the carbon number of the substituent is included.
  一般式（１）において、Ｙ1～Ｙ4はそれぞれ式（1a-1）～（1a-6）で表される。式（1a-1）～（1a-6）において、Ｒ1、Ｒ2及びＲ3はそれぞれ独立して水素、炭素数１～１０のアルキル基、炭素数３～１１のシクロアルキル基、炭素数６～１２の芳香族炭化水素基又は炭素数３～１１の芳香族複素環基を表す。好ましくは水素、炭素数１～４のアルキル基、炭素数３～６のシクロアルキル基、フェニル基、ナフチル基、カルバゾリル基、キノリル基、イソキノリル基である。そして、より好ましくは水素、フェニル基又はカルバゾリル基である。 In the general formula (1), Y 1 to Y 4 are represented by the formulas (1a-1) to (1a-6), respectively. In formulas (1a-1) to (1a-6), R 1 , R 2 and R 3 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 11 carbon atoms, Represents a 6-12 aromatic hydrocarbon group or a C3-C11 aromatic heterocyclic group. Preferred are hydrogen, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a naphthyl group, a carbazolyl group, a quinolyl group, and an isoquinolyl group. And more preferably, they are hydrogen, a phenyl group, or a carbazolyl group.
  また、式（1a-1）、（1a-2）、（1a-4）及び（1a-6）において、Ｒ3はインドロカルバゾール骨格を形成する中央の六員環とで縮合環を形成しても良い。上記六員環とＲ3が縮合する場合、Ｒ3は縮合環であってもよい。縮合環である場合はインドール環が好ましく、この場合、ジインドロカルバゾールを形成することになる。このとき、該インドール環は置換基を有してもよい。Ｒ3が上記六員環に縮合する基である場合、縮合し形成された縮合環から上記六員環を除いた環としては、ピロール環、フラン環、チオフェン環、インドール環、ベンゾフラン環、ベンゾチオフェン環、ベンゼン環、ナフタレン環等であることができる。これらの環は置換基を有しても良く、好ましくは、置換基を有してもよいインドール環であり、その場合上記六員環を含めるとカルバゾール環を形成することがよい。Ｒ3が上記六員環と縮合する場合は、Ｒ3が上記六員環に置換する位置の隣接位の炭素が置換可能な水素を有する場合である。 In the formulas (1a-1), (1a-2), (1a-4) and (1a-6), R 3 forms a condensed ring with the central six-membered ring forming the indolocarbazole skeleton. May be. When the six-membered ring and R 3 are condensed, R 3 may be a condensed ring. In the case of a condensed ring, an indole ring is preferable, and in this case, diindolocarbazole is formed. At this time, the indole ring may have a substituent. When R 3 is a group that condenses on the six-membered ring, the ring obtained by removing the six-membered ring from the condensed ring formed by condensation includes a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, It can be a thiophene ring, a benzene ring, a naphthalene ring or the like. These rings may have a substituent, and are preferably indole rings which may have a substituent. In this case, when the 6-membered ring is included, a carbazole ring may be formed. If R 3 is condensed with the six-membered ring is a case where R 3 has a substitutable hydrogen atoms of the adjacent position is substituted position on the six-membered ring.
  Ａは独立に１価の炭素数１～１０のアルキル基、炭素数３～１１のシクロアルキル基、炭素数６～５０の芳香族炭化水素基又は炭素数３～５０の芳香族複素環基を示す。好ましいＡの具体例としては、ベンゼン、ナフタレン、フルオレン、アントラセン、フェナントレン、フルオランテン、ピレン、クリセン、ピリジン、ピリミジン、トリアジン、キノリン、イソキノリン、キノキサリン、ナフチリジン、カルバゾール、アクリジン又はこれらが複数連結された芳香族化合物から水素を除いて生じる１価の基が挙げられる。より好ましくは、ベンゼン、ピリジン、ピリミジン、トリアジン、ナフタレン、カルバゾール又はこれらが複数連結された芳香族化合物から水素を除いて生じる１価の基が挙げられる。上記芳香族化合物が複数連結される場合、それらは同一でも異なっていてもよい。上記複数連結された芳香族化合物から水素を除いて生じる基の具体例としては、例えばビフェニル、ターフェニル、ビピリジン、ビピリミジン、ビトリアジン、ビストリアジルベンゼン、フェニルピリジン、ジフェニルピリジン、ジフェニルピリミジン、ジフェニルトリアジン、フェニルカルバゾール、ピリジルカルバゾール等から生じる１価の基が挙げられる。上記アルキル基、シクロアルキル基、芳香族炭化水素基又は芳香族複素環基は置換基を有してもよく、置換基を有する場合、好ましい置換基としては、炭素数１～４のアルキル基、炭素数１～２のアルコキシ基、アセチル基、炭素数６～１８のアリール基、炭素数３～１７のヘテロアリール基である。より好ましくは、フェニル基、ナフチル基、カルバゾリル基、キノリル基、イソキノリル基である。また、式（1a-1）～（1a-6）のＮとのＡの置換位置は限定されない。 A is independently a monovalent alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 11 carbon atoms, an aromatic hydrocarbon group having 6 to 50 carbon atoms, or an aromatic heterocyclic group having 3 to 50 carbon atoms. Show. Specific examples of preferred A include benzene, naphthalene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, chrysene, pyridine, pyrimidine, triazine, quinoline, isoquinoline, quinoxaline, naphthyridine, carbazole, acridine, or aromatics in which a plurality of these are linked. A monovalent group generated by removing hydrogen from a compound can be mentioned. More preferably, a monovalent group produced by removing hydrogen from benzene, pyridine, pyrimidine, triazine, naphthalene, carbazole or an aromatic compound in which a plurality of these are linked is used. When a plurality of the aromatic compounds are connected, they may be the same or different. Specific examples of the group generated by removing hydrogen from the above-described aromatic compounds linked together include, for example, biphenyl, terphenyl, bipyridine, bipyrimidine, bitriazine, bistriazylbenzene, phenylpyridine, diphenylpyridine, diphenylpyrimidine, diphenyltriazine, phenyl And monovalent groups derived from carbazole, pyridylcarbazole and the like. The alkyl group, cycloalkyl group, aromatic hydrocarbon group or aromatic heterocyclic group may have a substituent, and when it has a substituent, preferred substituents include alkyl groups having 1 to 4 carbon atoms, An alkoxy group having 1 to 2 carbon atoms, an acetyl group, an aryl group having 6 to 18 carbon atoms, and a heteroaryl group having 3 to 17 carbon atoms. More preferred are a phenyl group, a naphthyl group, a carbazolyl group, a quinolyl group, and an isoquinolyl group. Further, the substitution position of A with N in the formulas (1a-1) to (1a-6) is not limited.
  一般式（１）において、ｍは１～３の整数を表す。好ましくは、ｍは１～２の整数であり、より好ましくは、ｍは１である。 In general formula (1), m represents an integer of 1 to 3. Preferably, m is an integer from 1 to 2, and more preferably, m is 1.
  一般式（１）において、ｎは１～３の整数を表す。好ましくは、ｎは１～２の整数であり、より好ましくは、ｎは１である。 In general formula (1), n represents an integer of 1 to 3. Preferably, n is an integer from 1 to 2, more preferably n is 1.
  一般式（１）において、ｐは０～３の整数を表す。好ましくは、ｐは０～２の整数であり、より好ましくは、ｐは０又は１である。 In general formula (1), p represents an integer of 0-3. Preferably, p is an integer from 0 to 2, more preferably, p is 0 or 1.
  一般式（１）において、ｑは０～３の整数を表す。好ましくは、ｑは０～２の整数であり、より好ましくは、ｑは０又は１である。 In general formula (1), q represents an integer of 0-3. Preferably, q is an integer from 0 to 2, and more preferably q is 0 or 1.
  一般式（１）において、ｍ、ｎ、ｐ及びｑの総和は２～６の整数である。好ましくは２～４であり、より好ましくは２又は３である。 In general formula (1), the sum of m, n, p and q is an integer of 2-6. It is preferably 2 to 4, more preferably 2 or 3.
  一般式（１）で表されるインドロカルバゾール化合物の中でも、上記一般式（２）～（７）で表されるインドロカルバゾール化合物が好ましい化合物として挙げられる。 Among the indolocarbazole compounds represented by the general formula (1), the indolocarbazole compounds represented by the above general formulas (2) to (7) are preferable compounds.
  一般式（１）～（７）及び式（1a-1）～（1a-6）において、それぞれ同一の記号及び式は特に断らない限り同一の意味を有すると解される。一般式（２）～（７）において、ｍ及びｎはそれぞれ１又は２であることが好ましく、ｍ及びｎがそれぞれ１であることがより好ましい。 In general formulas (1) to (7) and formulas (1a-1) to (1a-6), the same symbols and formulas are understood to have the same meaning unless otherwise specified. In the general formulas (2) to (7), m and n are each preferably 1 or 2, and more preferably m and n are each 1.
  一般式（１）～（７）で表されるインドロカルバゾール化合物は、目的とする化合物の構造に応じて原料を選択し、公知の手法を用いて合成することができる。 イ ン ド Indolocarbazole compounds represented by the general formulas (1) to (7) can be synthesized by selecting a raw material according to the structure of the target compound and using a known method.
  例えば、式（1a-1）で表されるインドロカルバゾール骨格Synlett，2005，No.1，p42-48に示される合成例を参考にして以下の反応式により合成することができる。 For example, it can be synthesized by the following reaction formula with reference to synthesis examples shown in the indolocarbazole skeleton Synlett, 2005, No. 1, p42-48 represented by the formula (1a-1).
Figure JPOXMLDOC01-appb-I000011
 
Figure JPOXMLDOC01-appb-I000011
 
  また、式（1a-2）で表されるインドロカルバゾール骨格を与えるインドロカルバゾール化合物は、Archiv der Pharmazie (Weinheim, Germany) 1987, 320(3), p280-2に示される合成例を参考にして以下の反応式により合成することができる。 Indolocarbazole compounds that give an indolocarbazole skeleton represented by the formula (1a-2) can be obtained by referring to the synthesis examples shown in Archiv der Pharmazie (Weinheim, Germany) 1987, 320 (3), p280-2. Can be synthesized by the following reaction formula.
　　
Figure JPOXMLDOC01-appb-I000012
  　　
Figure JPOXMLDOC01-appb-I000012
 
  更に、式（1a-3）及び式（1a-4）で表されるインドロカルバゾール骨格を与えるインドロカルバゾール化合物は、The Journal of Organic Chemistry，2007,72（15）5886並びに、Tetrahedron, 1999, 55, p2371に示される合成例を参考にして以下の反応式により合成することができる。 Furthermore, indolocarbazole compounds that give an indolocarbazole skeleton represented by formula (1a-3) and formula (1a-4) are The Journal of Organic Chemistry, 2007,72 (15) 5886 and Tetrahedron, 1999, It can be synthesized by the following reaction formula with reference to the synthesis example shown in p.
Figure JPOXMLDOC01-appb-I000013
 
Figure JPOXMLDOC01-appb-I000013
 
  前述の反応式で得られる各インドロカルバゾール化合物の窒素に結合する水素を、定法に従い、対応する芳香族基に置換させ、カップリングすることで、一般式（１）又は（２）～（７）で表される化合物群を合成することができる。 By substituting the hydrogen bonded to the nitrogen of each indolocarbazole compound obtained by the above reaction formula with a corresponding aromatic group according to a conventional method and coupling, the general formula (1) or (2) to (7) ) Can be synthesized.
  一般式（１）で表されるインドロカルバゾール化合物の具体例を以下に示すが、本発明の有機電界発光素子において使用されるインドロカルバゾール化合物はこれらに限定されない。 Specific examples of the indolocarbazole compound represented by the general formula (1) are shown below, but the indolocarbazole compound used in the organic electroluminescence device of the present invention is not limited thereto.
　　
Figure JPOXMLDOC01-appb-I000014
  　　
Figure JPOXMLDOC01-appb-I000014
 
Figure JPOXMLDOC01-appb-I000015
 
Figure JPOXMLDOC01-appb-I000015
 
　　
Figure JPOXMLDOC01-appb-I000016
  　　
Figure JPOXMLDOC01-appb-I000016
 
　　
Figure JPOXMLDOC01-appb-I000017
  　　
Figure JPOXMLDOC01-appb-I000017
 
　　
Figure JPOXMLDOC01-appb-I000018
  　　
Figure JPOXMLDOC01-appb-I000018
 
Figure JPOXMLDOC01-appb-I000019
 
Figure JPOXMLDOC01-appb-I000019
 
Figure JPOXMLDOC01-appb-I000020
 
Figure JPOXMLDOC01-appb-I000020
 
Figure JPOXMLDOC01-appb-I000021
 
Figure JPOXMLDOC01-appb-I000021
 
Figure JPOXMLDOC01-appb-I000022
 
Figure JPOXMLDOC01-appb-I000022
 
Figure JPOXMLDOC01-appb-I000023
 
Figure JPOXMLDOC01-appb-I000023
 
Figure JPOXMLDOC01-appb-I000024
 
Figure JPOXMLDOC01-appb-I000024
 
Figure JPOXMLDOC01-appb-I000025
 
Figure JPOXMLDOC01-appb-I000025
 
Figure JPOXMLDOC01-appb-I000026
 
Figure JPOXMLDOC01-appb-I000026
 

Figure JPOXMLDOC01-appb-I000027
 
Figure JPOXMLDOC01-appb-I000027
 
Figure JPOXMLDOC01-appb-I000028
 
Figure JPOXMLDOC01-appb-I000028
 
Figure JPOXMLDOC01-appb-I000029
 
Figure JPOXMLDOC01-appb-I000029
 
Figure JPOXMLDOC01-appb-I000030
 
Figure JPOXMLDOC01-appb-I000030
 

Figure JPOXMLDOC01-appb-I000031
 
Figure JPOXMLDOC01-appb-I000031
 

Figure JPOXMLDOC01-appb-I000032
 
Figure JPOXMLDOC01-appb-I000032
 
Figure JPOXMLDOC01-appb-I000033
 
Figure JPOXMLDOC01-appb-I000033
 
  上記一般式（１）で表されるインドロカルバゾール化合物は、基板上に、陽極、複数の有機層及び陰極が積層されてなる有機ＥＬ素子の少なくとも１つの有機層に含有させることにより、優れた有機電界発光素子を与える。含有させる有機層としては、発光層、正孔輸送層、電子輸送層又は正孔阻止層が適する。より好ましくは、燐光発光ドーパントを含有する発光層のホスト材料として含有させることがよい。 The indolocarbazole compound represented by the general formula (1) is excellent by being contained in at least one organic layer of an organic EL device in which an anode, a plurality of organic layers and a cathode are laminated on a substrate. An organic electroluminescent device is provided. As the organic layer to be contained, a light emitting layer, a hole transport layer, an electron transport layer or a hole blocking layer is suitable. More preferably, it may be contained as a host material of a light emitting layer containing a phosphorescent dopant.
  次に、本発明の有機ＥＬ素子について説明する。 Next, the organic EL element of the present invention will be described.
  本発明の有機ＥＬ素子は、基板上に積層された陽極と陰極の間に、少なくとも一つの発光層を有する有機層を有し、且つ少なくとも一つの有機層は、上記インドロカルバゾール化合物を含む。有利には、燐光発光ドーパントと共に上記インドロカルバゾール化合物を発光層中に含む。 The organic EL device of the present invention has an organic layer having at least one light emitting layer between an anode and a cathode laminated on a substrate, and at least one organic layer contains the indolocarbazole compound. Advantageously, the indolocarbazole compound is included in the light emitting layer together with a phosphorescent dopant.
  次に、本発明の有機ＥＬ素子の構造について、図面を参照しながら説明するが、本発明の有機ＥＬ素子の構造は何ら図示のものに限定されるものではない。 Next, the structure of the organic EL element of the present invention will be described with reference to the drawings. However, the structure of the organic EL element of the present invention is not limited to the illustrated one.
  図１は本発明に用いられる一般的な有機ＥＬ素子の構造例を示す断面図であり、１は基板、２は陽極、３は正孔注入層、４は正孔輸送層、５は発光層、６は電子輸送層、７は陰極を各々表わす。本発明の有機ＥＬ素子では発光層と隣接して励起子阻止層を有してもよく、また、発光層と正孔注入層との間に電子阻止層を有しても良い。励起子阻止層は発光層の陽極側、陰極側のいずれにも挿入することができ、両方同時に挿入することも可能である。本発明の有機ＥＬ素子では、基板、陽極、発光層及び陰極を必須の層として有するが、必須の層以外の層に、正孔注入輸送層、電子注入輸送層を有することがよく、更に発光層と電子注入輸送層の間に正孔阻止層を有することがよい。なお、正孔注入輸送層は、正孔注入層と正孔輸送層のいずれか又は両者を意味し、電子注入輸送層は、電子注入層と電子輸送層のいずれか又は両者を意味する。 FIG. 1 is a cross-sectional view showing a structural example of a general organic EL device used in the present invention, wherein 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, and 5 is a light emitting layer. , 6 represents an electron transport layer, and 7 represents a cathode. The organic EL device of the present invention may have an exciton blocking layer adjacent to the light emitting layer, and may have an electron blocking layer between the light emitting layer and the hole injection layer. The exciton blocking layer can be inserted on either the anode side or the cathode side of the light emitting layer, or both can be inserted simultaneously. The organic EL device of the present invention has a substrate, an anode, a light emitting layer and a cathode as essential layers, but it is preferable to have a hole injecting and transporting layer and an electron injecting and transporting layer in layers other than the essential layers, and further emit light. It is preferable to have a hole blocking layer between the layer and the electron injecting and transporting layer. The hole injection / transport layer means either or both of a hole injection layer and a hole transport layer, and the electron injection / transport layer means either or both of an electron injection layer and an electron transport layer.
  なお、図１とは逆の構造、すなわち、基板１上に陰極７、電子輸送層６、発光層５、正孔輸送層４、陽極２の順に積層することも可能であり、この場合も、必要により層を追加したり、省略したりすることが可能である。 In addition, it is also possible to laminate | stack the cathode 7, the electron carrying layer 6, the light emitting layer 5, the positive hole transport layer 4, and the anode 2 in order on the board | substrate 1 in the reverse structure, FIG. Layers can be added or omitted as necessary.
－基板－
  本発明の有機ＥＬ素子は、基板に支持されていることが好ましい。この基板については、特に制限はなく、従来から有機ＥＬ素子に慣用されているものであればよく、例えば、ガラス、透明プラスチック、石英などからなるものを用いることができる。 -substrate-
The organic EL element of the present invention is preferably supported on a substrate. The substrate is not particularly limited as long as it is conventionally used for an organic EL element. For example, a substrate made of glass, transparent plastic, quartz, or the like can be used.
－陽極－
  有機ＥＬ素子における陽極としては、仕事関数の大きい（４ｅＶ以上）金属、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが好ましく用いられる。このような電極物質の具体例としてはＡｕ等の金属、ＣｕＩ、インジウムチンオキシド（ＩＴＯ）、ＳｎＯ2、ＺｎＯ等の導電性透明材料が挙げられる。また、ＩＤＩＸＯ（Ｉｎ2Ｏ3－ＺｎＯ）等非晶質で透明導電膜を作製可能な材料を用いてもよい。陽極はこれらの電極物質を蒸着やスパッタリング等の方法により、薄膜を形成させ、フォトリソグラフィー法で所望の形状のパターンを形成してもよく、あるいはパターン精度をあまり必要としない場合は（１００μｍ以上程度）、上記電極物質の蒸着やスパッタリング時に所望の形状のマスクを介してパターンを形成してもよい。あるいは、有機導電性化合物のように塗布可能な物質を用いる場合には、印刷方式、コーティング方式等湿式成膜法を用いることもできる。この陽極より発光を取り出す場合には、透過率を１０％より大きくすることが望ましく、また陽極としてのシート抵抗は数百Ω／□以下が好ましい。更に膜厚は材料にもよるが、通常１０～１０００ｎｍ、好ましくは１０～２００ｎｍの範囲で選ばれる。 -anode-
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 and ZnO. Alternatively, an amorphous material such as IDIXO (In 2 O 3 —ZnO) that can form a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not required (about 100 μm or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
－陰極－
  一方、陰極としては、仕事関数の小さい（４ｅＶ以下）金属（電子注入性金属と称する）、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが用いられる。このような電極物質の具体例としては、ナトリウム、ナトリウム－カリウム合金、マグネシウム、リチウム、マグネシウム／銅混合物、マグネシウム／銀混合物、マグネシウム／アルミニウム混合物、マグネシウム／インジウム混合物、アルミニウム／酸化アルミニウム（Ａｌ2Ｏ3）混合物、インジウム、リチウム／アルミニウム混合物、希土類金属等が挙げられる。これらの中で、電子注入性及び酸化等に対する耐久性の点から、電子注入性金属とこれより仕事関数の値が大きく安定な金属である第二金属との混合物、例えば、マグネシウム／銀混合物、マグネシウム／アルミニウム混合物、マグネシウム／インジウム混合物、アルミニウム／酸化アルミニウム（Ａｌ2Ｏ3）混合物、リチウム／アルミニウム混合物、アルミニウム等が好適である。陰極はこれらの電極物質を蒸着やスパッタリング等の方法により薄膜を形成させることにより、作製することができる。また、陰極としてのシート抵抗は数百Ω／□以下が好ましく、膜厚は通常１０ｎｍ～５μｍ、好ましくは５０～２００ｎｍの範囲で選ばれる。なお、発光した光を透過させるため、有機ＥＬ素子の陽極又は陰極のいずれか一方が、透明又は半透明であれば発光輝度が向上し好都合である。 -cathode-
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum and the like. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.
  また、陰極に上記金属を１～２０ｎｍの膜厚で作製した後に、陽極の説明で挙げた導電性透明材料をその上に作製することで、透明又は半透明の陰極を作製することができ、これを応用することで陽極と陰極の両方が透過性を有する素子を作製することができる。 In addition, a transparent or semi-transparent cathode can be produced by producing the conductive transparent material mentioned in the description of the anode on the cathode after producing the metal with a thickness of 1 to 20 nm on the cathode. By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.
－発光層－
  発光層は燐光発光層であり、燐光発光ドーパントとホスト材料を含む。燐光発光ドーパント材料としては、ルテニウム、ロジウム、パラジウム、銀、レニウム、オスミウム、イリジウム、白金及び金から選ばれる少なくとも一つの金属を含む有機金属錯体を含有するものがよい。かかる有機金属錯体は、前記先行技術文献等で公知であり、これらが選択されて使用可能である。 -Light emitting layer-
The light emitting layer is a phosphorescent light emitting layer and includes a phosphorescent dopant and a host material. The phosphorescent dopant material preferably contains an organometallic complex containing at least one metal selected from ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum and gold. Such organometallic complexes are known in the prior art documents and the like, and these can be selected and used.
  好ましい燐光発光ドーパントとしては、Ir等の貴金属元素を中心金属として有するIr(ppy)3等の錯体類、(Bt)2Iracac等の錯体類、(Btp)Ptacac等の錯体類が挙げられる。これらの錯体類の具体例を以下に示すが、下記の化合物に限定されない。 Preferable phosphorescent dopants include complexes such as Ir (ppy) 3 having a noble metal element such as Ir as a central metal, complexes such as (Bt) 2 Iracac, and complexes such as (Btp) Ptacac. Specific examples of these complexes are shown below, but are not limited to the following compounds.
Figure JPOXMLDOC01-appb-I000034
 
Figure JPOXMLDOC01-appb-I000034
 
Figure JPOXMLDOC01-appb-I000035
 
Figure JPOXMLDOC01-appb-I000035
 
  前記燐光発光ドーパントが発光層中に含有される量は、５～３０重量％の範囲にあることが好ましい。 The amount of the phosphorescent dopant contained in the light emitting layer is preferably in the range of 5 to 30% by weight.
  発光層におけるホスト材料としては、前記一般式（１）で表されるインドロカルバゾール化合物を用いることが好ましい。しかし、該インドロカルバゾール化合物を発光層以外の他の何れかの有機層に使用する場合は、発光層に使用する材料はインドロカルバゾール化合物以外の他のホスト材料であってもよい。また、インドロカルバゾール化合物と他のホスト材料を併用してもよい。更に、公知のホスト材料を複数種類併用して用いてもよい。 As the host material in the light emitting layer, it is preferable to use an indolocarbazole compound represented by the general formula (1). However, when the indolocarbazole compound is used in any organic layer other than the light emitting layer, the material used for the light emitting layer may be a host material other than the indolocarbazole compound. An indolocarbazole compound and another host material may be used in combination. Furthermore, a plurality of known host materials may be used in combination.
  使用できる公知のホスト化合物としては、正孔輸送能、電子輸送能を有し、かつ発光の長波長化を防ぎ、なおかつ高いガラス転移温度を有する化合物であることが好ましい。 A known host compound that can be used is preferably a compound that has a hole transporting ability and an electron transporting ability, prevents a long wavelength of light emission, and has a high glass transition temperature.
  このような他のホスト材料は、多数の特許文献等により知られているので、それらから選択することができる。ホスト材料の具体例としては、特に限定されるものではないが、インドール誘導体、カルバゾール誘導体、トリアゾール誘導体、オキサゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体、ピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、芳香族第三アミン化合物、スチリルアミン化合物、芳香族ジメチリデン系化合物、ポルフィリン系化合物、アントラキノジメタン誘導体、アントロン誘導体、ジフェニルキノン誘導体、チオピランジオキシド誘導体、ナフタレンペリレン等の複素環テトラカルボン酸無水物、フタロシアニン誘導体、８―キノリノール誘導体の金属錯体やメタルフタロシアニン、ベンゾオキサゾールやベンゾチアゾール誘導体の金属錯体に代表される各種金属錯体、ポリシラン系化合物、ポリ（N-ビニルカルバゾール）誘導体、アニリン系共重合体、チオフェンオリゴマー、ポリチオフェン誘導体、ポリフェニレン誘導体、ポリフェニレンビニレン誘導体、ポリフルオレン誘導体等の高分子化合物等が挙げられる。 Such other host materials are known from a large number of patent documents and can be selected from them. Specific examples of the host material are not particularly limited, but include indole derivatives, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine. Derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, anthraquino Heterocyclic tetracarboxylic acid anhydrides such as dimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, Various metal complexes typified by metal complexes of Russianine derivatives, 8-quinolinol derivatives, metal phthalocyanines, metal complexes of benzoxazole and benzothiazole derivatives, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline copolymers, Examples thereof include polymer compounds such as thiophene oligomers, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives, and the like.
－注入層－
  注入層とは、駆動電圧低下や発光輝度向上のために電極と有機層間に設けられる層のことで、正孔注入層と電子注入層があり、陽極と発光層又は正孔輸送層の間、及び陰極と発光層又は電子輸送層との間に存在させてもよい。注入層は必要に応じて設けることができる。 -Injection layer-
The injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of light emission. There are a hole injection layer and an electron injection layer, and between the anode and the light emitting layer or the hole transport layer. And between the cathode and the light emitting layer or the electron transport layer. The injection layer can be provided as necessary.
－正孔阻止層－
  正孔阻止層とは広い意味では電子輸送層の機能を有し、電子を輸送する機能を有しつつ正孔を輸送する能力が著しく小さい正孔阻止材料からなり、電子を輸送しつつ正孔を阻止することで電子と正孔の再結合確率を向上させることができる。 -Hole blocking layer-
The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking.
  正孔阻止層には一般式（１）で表されるインドロカルバゾール化合物を用いることが好ましいが、インドロカルバゾール化合物を他の何れかの有機層に使用する場合は、公知の正孔阻止層材料を用いてもよい。また、正孔阻止層材料としては、後述する電子輸送層の材料を必要に応じて用いることができる。 It is preferable to use the indolocarbazole compound represented by the general formula (1) for the hole blocking layer. However, when the indolocarbazole compound is used for any other organic layer, a known hole blocking layer is used. Materials may be used. Moreover, as a hole-blocking layer material, the material of the electron carrying layer mentioned later can be used as needed.
－電子阻止層－
  電子阻止層とは、正孔を輸送する機能を有しつつ電子を輸送する能力が著しく小さい材料から成り、正孔を輸送しつつ電子を阻止することで電子と正孔が再結合する確率を向上させることができる。 -Electron blocking layer-
The electron blocking layer is made of a material that has a function of transporting holes and has a very small ability to transport electrons. The electron blocking layer blocks the electrons while transporting holes, and the probability of recombination of electrons and holes. Can be improved.
  電子阻止層の材料としては、本発明に係る一般式（１）で表されるインドロカルバゾール化合物を用いることができるが、他の材料として、後述する正孔輸送層の材料を必要に応じて用いることもできる。電子阻止層の膜厚は好ましくは３～１００ｎｍであり、より好ましくは５～３０ｎｍである。 As the material for the electron blocking layer, the indolocarbazole compound represented by the general formula (1) according to the present invention can be used. As other materials, the material for the hole transport layer described later is used as necessary. It can also be used. The thickness of the electron blocking layer is preferably 3 to 100 nm, more preferably 5 to 30 nm.
－励起子阻止層－
  励起子阻止層とは、発光層内で正孔と電子が再結合することにより生じた励起子が電荷輸送層に拡散することを阻止するための層であり、本層の挿入により励起子を効率的に発光層内に閉じ込めることが可能となり、素子の発光効率を向上させることができる。励起子阻止層は発光層に隣接して陽極側、陰極側のいずれにも挿入することができ、両方同時に挿入することも可能である。 -Exciton blocking layer-
The exciton blocking layer is a layer for preventing excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. It becomes possible to efficiently confine in the light emitting layer, and the light emission efficiency of the device can be improved. The exciton blocking layer can be inserted on either the anode side or the cathode side adjacent to the light emitting layer, or both can be inserted simultaneously.
  励起子阻止層の材料としては、一般式（１）で表されるインドロカルバゾール化合物を用いることができるが、他の材料として、例えば、１，３－ジカルバゾリルベンゼン（ｍＣＰ）や、ビス（２－メチル－８－キノリノラト）－４－フェニルフェノラトアルミニウム（III）（ＢＡｌｑ）が挙げられる。 As the material for the exciton blocking layer, an indolocarbazole compound represented by the general formula (1) can be used. As other materials, for example, 1,3-dicarbazolylbenzene (mCP), Bis (2-methyl-8-quinolinolato) -4-phenylphenolato aluminum (III) (BAlq).
－正孔輸送層－
  正孔輸送層とは正孔を輸送する機能を有する正孔輸送材料からなり、正孔輸送層は単層又は複数層設けることができる。 -Hole transport layer-
The hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer can be provided as a single layer or a plurality of layers.
  正孔輸送材料としては、正孔の注入又は輸送、電子の障壁性のいずれかを有するものであり、有機物、無機物のいずれであってもよい。正孔輸送層には一般式（１）で表されるインドロカルバゾール化合物を用いることが好ましいが、従来公知の化合物の中から任意のものを選択して用いることができる。使用できる公知の正孔輸送材料としては例えば、トリアゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体及びピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、オキサゾール誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、アニリン系共重合体、また導電性高分子オリゴマー、特にチオフェンオリゴマー等が挙げられるが、ポルフィリン化合物、芳香族第３級アミン化合物及びスチリルアミン化合物を用いることが好ましく、芳香族第３級アミン化合物を用いることがより好ましい。 The hole transport material has either hole injection or transport or electron barrier properties, and may be either organic or inorganic. Although it is preferable to use the indolocarbazole compound represented by General formula (1) for a positive hole transport layer, arbitrary things can be selected and used from a conventionally well-known compound. Examples of known hole transport materials that can be used include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, Examples include styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. Porphyrin compounds, aromatic tertiary amine compounds, and styryl. It is preferable to use an amine compound, and it is more preferable to use an aromatic tertiary amine compound.
－電子輸送層－
  電子輸送層とは電子を輸送する機能を有する材料からなり、電子輸送層は単層又は複数層設けることができる。 -Electron transport layer-
The electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer can be provided as a single layer or a plurality of layers.
  電子輸送材料（正孔阻止材料を兼ねる場合もある）としては、陰極より注入された電子を発光層に伝達する機能を有していればよい。電子輸送層には本発明に係る一般式（１）で表される材料を用いることが好ましいが、従来公知の化合物の中から任意のものを選択して用いることができ、例えば、ニトロ置換フルオレン誘導体、ジフェニルキノン誘導体、チオピランジオキシド誘導体、カルボジイミド、フレオレニリデンメタン誘導体、アントラキノジメタン及びアントロン誘導体、オキサジアゾール誘導体等が挙げられる。更に、上記オキサジアゾール誘導体において、オキサジアゾール環の酸素原子を硫黄原子に置換したチアジアゾール誘導体、電子吸引基として知られているキノキサリン環を有するキノキサリン誘導体も、電子輸送材料として用いることができる。更にこれらの材料を高分子鎖に導入した、又はこれらの材料を高分子の主鎖とした高分子材料を用いることもできる。 As an electron transport material (which may also serve as a hole blocking material), it is sufficient if it has a function of transmitting electrons injected from the cathode to the light emitting layer. Although it is preferable to use the material represented by the general formula (1) according to the present invention for the electron transport layer, any one of conventionally known compounds can be selected and used. For example, nitro-substituted fluorene Derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  以下、本発明を実施例によって更に詳しく説明するが、本発明は勿論、これらの実施例に限定されるものではなく、その要旨を越えない限りにおいて、種々の形態で実施することが可能である。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is of course not limited to these examples, and can be implemented in various forms as long as the gist thereof is not exceeded. .
  以下に示すルートによりインドロカルバゾール化合物を合成した。尚、化合物番号は、上記化学式に付した番号に対応する。 イ ン ド Indolocarbazole compounds were synthesized by the route shown below. The compound number corresponds to the number assigned to the above chemical formula.
合成例１
化合物３－１５の合成
Figure JPOXMLDOC01-appb-I000036
  Synthesis example 1
Synthesis of Compound 3-15
Figure JPOXMLDOC01-appb-I000036
  窒素雰囲気下、1,2-シクロヘキサンジオン33.3 g (0.30 mol)、フェニルヒドラジン塩酸塩86.0 g (0.60 mol)とエタノール1000 mlを室温で撹拌しながら、濃硫酸3.0 g (0.031 mol)を5分かけて滴下した後に、65℃で加熱しながら4時間撹拌した。反応溶液を室温まで冷却した後に、析出した結晶をろ取し、エタノール(2 × 500 ml)を用いて洗浄を行い、紫茶色結晶80.0 gを得た。この結晶72.0 g (0.26 mol)、トリフルオロ酢酸72.0 gと酢酸720.0 gを100℃で加熱しながら15時間撹拌した。反応溶液を室温まで冷却した後に、析出した結晶をろ取し、酢酸(200 ml)で洗浄した。リスラリー精製を行い、白色結晶として5,12‐ジヒドロインドロ［2,3‐a］カルバゾール（IC-１） 30.0 g (収率45 %)を得た。 Concentrated sulfuric acid 3.0 g (0.031 mol) over 5 minutes while stirring 33.3 シ ク ロ ヘ キ サ ン g (0.30 mol) of 1,2-cyclohexanedione, 86.0 g (0.60 mol) of phenylhydrazine hydrochloride and 1000 ml of ethanol at room temperature under nitrogen atmosphere Then, the mixture was stirred for 4 hours while being heated at 65 ° C. After the reaction solution was cooled to room temperature, the precipitated crystals were collected by filtration and washed with ethanol (2 × 500 ml) to obtain 80.0 g of purple brown crystals. 72.0 g of the crystals (0.26 mol), 72.0 g of trifluoroacetic acid and 720.0 g of acetic acid were stirred for 15 hours while heating at 100 ° C. After the reaction solution was cooled to room temperature, the precipitated crystals were collected by filtration and washed with acetic acid (200 ml). Re-slurry purification was performed to obtain 3,12-dihydroindolo [2,3-a] carbazole (IC-1) 30.0 g (yield 45%) as white crystals.
Figure JPOXMLDOC01-appb-I000037
 
Figure JPOXMLDOC01-appb-I000037
 
  窒素雰囲気下、インドール20.0 g (0.17 mol)の脱水ジエチルエーテル300 ml溶液を室温で撹拌しながら、濃硫酸211.7 g (2.16 mol)に濃塩酸112.0 g (1.10 mol)を1時間かけて滴下し発生させた塩化水素ガスを吹き込んだ。反応溶液を室温で15時間撹拌した後に、酢酸エチル121.0 gと飽和炭酸水素ナトリウム水溶液303.2 gを加えた。水層を酢酸エチル(2 × 100 ml)で抽出した後に、有機層を飽和炭酸水素ナトリウム水溶液(100 ml)と蒸留水(2 × 100 ml)で洗浄した。有機層を無水硫酸マグネシウムで乾燥した後に、硫酸マグネシウムをろ別し、溶媒を減圧留去した。得られた残渣をトルエン150 mlに溶解し、パラジウム/活性炭2.5 gを加えた後に、111℃で加熱還流しながら3時間撹拌した。反応溶液を室温まで冷却した後に、パラジウム/活性炭をろ別し、溶媒を減圧留去した。再結晶により精製を行い、白色結晶として中間体Ａ14.7 g(収率37 %)を得た。 Concentrated hydrochloric acid 112.0 g (1.10 mol) was added dropwise over 21 hours to 211.7 g (2.16 mol) of concentrated sulfuric acid while stirring a solution of indium 20.0 g (0.17 mol) in 300 ml of dehydrated diethyl ether at room temperature in a nitrogen atmosphere. Injected hydrogen chloride gas. After stirring the reaction solution at room temperature for 15 hours, 121.0 g of ethyl acetate and 303.2 g of saturated aqueous sodium hydrogen carbonate solution were added. The aqueous layer was extracted with ethyl acetate (2 × 100 ml), and the organic layer was washed with saturated aqueous sodium hydrogen carbonate solution (100 ml) and distilled water (2 × 100 ml). After the organic layer was dried over anhydrous magnesium sulfate, magnesium sulfate was filtered off and the solvent was distilled off under reduced pressure. The obtained residue was dissolved in 150 ml of toluene and 2.5 g of palladium / activated carbon was added, followed by stirring for 3 hours while heating at 111 ° C. under reflux. After cooling the reaction solution to room temperature, palladium / activated carbon was filtered off and the solvent was distilled off under reduced pressure. Purification was performed by recrystallization to obtain 14.7 g of intermediate A as white crystals (yield 37%).
　　
Figure JPOXMLDOC01-appb-I000038
  　　
Figure JPOXMLDOC01-appb-I000038
 
  窒素雰囲気下、中間体Ａ 14.1 g (0.061 mol)、N,N'-ジメチルアミノアセトアルデヒドジエチルアセタール11.4 g (0.071 mol)と酢酸110.0 gを118℃で加熱還流しながら8時間撹拌した。反応溶液を室温まで冷却した後に、析出した結晶をろ取し、酢酸(30 ｍl)で洗浄した。得られた結晶をリスラリー精製し、白色結晶として5,12‐ジヒドロインドロ［3,2‐a］カルバゾール（IC－2） 10.4 g (収率67 %)を得た。 Under a nitrogen atmosphere, intermediate A 14.1 g (0.061 mol), N, N'-dimethylaminoacetaldehyde diethyl acetal 11.4 g (0.071 mol) and 110.0 g acetic acid were stirred at 118 ° C. for 8 hours with heating under reflux. After the reaction solution was cooled to room temperature, the precipitated crystals were collected by filtration and washed with acetic acid (30 ml). The obtained crystals were purified by reslurry to obtain 5,12-dihydroindolo [3,2-a] carbazole (IC-2) 10.4 g (yield 67%) as white crystals.
　　
Figure JPOXMLDOC01-appb-I000039
  　　
Figure JPOXMLDOC01-appb-I000039
 
  窒素雰囲気下、化合物（IC－2） 10.0 g（0.039 mol）、ヨードベンゼン39.8 g（0.20 mol）、銅6.2g（0.098 mol）、炭酸カリウム8.1 g（0.059 mol）、テトラグライム200 mlを加えて撹拌した。その後190 ℃まで加熱し、24時間撹拌した。反応溶液を室温まで冷却した後に、銅、無機物をろ別した。ろ液に蒸留水200 mlを加えて撹拌し、析出した結晶をろ別した。これを減圧乾燥した後、カラムクロマトグラフィーで精製して白色粉末の中間体Ｂ 9.7 g（0.029 mol、収率75 %）を得た。 In a nitrogen atmosphere, add compound (IC-2) 10.0 g (0.039 mol), iodobenzene 39.8 g (0.20 mol), copper 6.2g (0.098gmol), potassium carbonate 8.1 g (0.059 mol), tetraglyme 200 ml. Stir. Thereafter, the mixture was heated to 190 ° C. and stirred for 24 hours. After cooling the reaction solution to room temperature, copper and inorganic substances were separated by filtration. 200 ml of distilled water was added to the filtrate and stirred, and the precipitated crystals were filtered off. This was dried under reduced pressure and then purified by column chromatography to obtain 9.7 g (0.029 mol, yield 75%) of Intermediate B as a white powder.

Figure JPOXMLDOC01-appb-I000040
 
Figure JPOXMLDOC01-appb-I000040
 
  窒素雰囲気下、化合物（IC－1） 26.0 g (0.10 mol)、ヨードベンゼン122.7 g (0.60 mol)、ヨウ化銅54.7 g (0.29 mol)、炭酸カリウム66.7 g (0.48 mol)とキノリン800 mlを190℃で加熱しながら72時間撹拌した。反応溶液を室温まで冷却した後に、蒸留水(500 ml)とジクロロメタン(500 ml)を撹拌しながら加えた。析出した結晶をろ別した後に、有機層を蒸留水(3 × 500 ml)で洗浄した。有機層を無水硫酸マグネシウムで乾燥した後に、硫酸マグネシウムをろ別し、溶媒を減圧留去した。得られた残渣をシリカゲルカラムクロマトグラフィーで精製を行い、白色固体として中間体Ｃ 13.7 g (収率41 %)を得た。 Under nitrogen atmosphere, compound (IC-1) 26.0 g (0.10 mol), iodobenzene 122.7 g (0.60 mol), copper iodide 54.7 g (0.29 mol), potassium carbonate 66.7 g (0.48 mol) and quinoline 800 ml 190 The mixture was stirred for 72 hours while being heated at ° C. After the reaction solution was cooled to room temperature, distilled water (500 ml) and dichloromethane (500 ml) were added with stirring. After the precipitated crystals were filtered off, the organic layer was washed with distilled water (3 × 500 ml). After the organic layer was dried over anhydrous magnesium sulfate, magnesium sulfate was filtered off and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain 13.7 g of intermediate C (yield 41%) as a white solid.
Figure JPOXMLDOC01-appb-I000041
 
Figure JPOXMLDOC01-appb-I000041
 
  窒素雰囲気下、塩化シアヌル85.4g(0.46 mol)、脱水テトラヒドロフラン500 mlを加え、撹拌した。反応溶液の温度を-20℃以下に保ちながら1.1 mol/l臭化フェニルマグネシウム、テトラヒドロフラン溶液600 mlを1時間かけて滴下した後、1.5時間撹拌を続けた。その後、トルエン300 ml、2N HCl 500 mlを、反応溶液の温度を5 ℃以下に保ちながら加えた。反応溶液を有機層と水層に分画し、有機層を蒸留水（2×300ml）で洗浄し、更に飽和食塩水で一回洗浄した後、有機層を硫酸マグネシウムで脱水を行った。硫酸マグネシウムをろ別した後、溶媒を減圧留去した。得られた粘性のある液体にｎ－ヘキサン1000 gを加え、加熱、撹拌を行った。その後、熱時濾過を行い、不溶分を除去した。ろ液を冷却し、析出した針状結晶をろ取、乾燥し中間体Ｄ 73.3 g（0.32 mol、収率75 %）を得た。 Under a nitrogen atmosphere, 85.4 g (0.46 mol) of cyanuric chloride and 500 ml of dehydrated tetrahydrofuran were added and stirred. While maintaining the temperature of the reaction solution at −20 ° C. or lower, 1.1 μmol / l phenylmagnesium bromide and 600 ml of tetrahydrofuran solution were added dropwise over 1 hour, and then the stirring was continued for 1.5 hours. Thereafter, 300 ml of toluene and 500 ml of 2N HCl were added while keeping the temperature of the reaction solution at 5 ° C. or lower. The reaction solution was divided into an organic layer and an aqueous layer, and the organic layer was washed with distilled water (2 × 300 ml) and further washed once with a saturated saline solution, and then the organic layer was dehydrated with magnesium sulfate. After filtering off magnesium sulfate, the solvent was distilled off under reduced pressure. To the obtained viscous liquid, 1000 g of n-hexane was added, and the mixture was heated and stirred. Thereafter, hot filtration was performed to remove insoluble matters. The filtrate was cooled, and the precipitated needle crystals were collected by filtration and dried to obtain Intermediate D 73.3 g (0.32 mol, yield 75%).
Figure JPOXMLDOC01-appb-I000042
 
Figure JPOXMLDOC01-appb-I000042
 
  窒素雰囲気下、56 %水素化ナトリウム1.6 g、脱水N,N-ジメチルホルムアミド50 mlを加え、撹拌を行った。次に中間体Ｃ  10.0 g(0.030 mol)を脱水N,N-ジメチルホルムアミド60 mlに溶解させた溶液を30分かけて滴下した。その後、1時間撹拌を続けた。次に中間体Ｄ 7.0 g(0.031 mol) を脱水N,N-ジメチルホルムアミド60 mlに溶解させた溶液を30分かけて滴下した。その後、一昼夜撹拌を続けた。次に同フラスコ内に蒸留水300 gを加え、析出した黄色結晶をろ取した。ろ取した黄色結晶をリスラリー精製し、乾燥させ中間体Ｅ 15.0 g(0.029 mol、収率96 %)を得た。
APCI-TOFMS, m/z 523 [M+H]+ Under a nitrogen atmosphere, 1.6 g of 56% sodium hydride and 50 ml of dehydrated N, N-dimethylformamide were added and stirred. Next, a solution prepared by dissolving 10.0 g (0.030 mol) of Intermediate C in 60 ml of dehydrated N, N-dimethylformamide was added dropwise over 30 minutes. Thereafter, stirring was continued for 1 hour. Next, a solution prepared by dissolving 7.0 g (0.031 mol) of Intermediate D in 60 ml of dehydrated N, N-dimethylformamide was added dropwise over 30 minutes. Thereafter, stirring was continued for a whole day and night. Next, 300 g of distilled water was added to the flask, and the precipitated yellow crystals were collected by filtration. The yellow crystals collected by filtration were reslurried and dried to obtain 15.0 g of Intermediate E (0.029 mol, yield 96%).
APCI-TOFMS, m / z 523 [M + H] +
Figure JPOXMLDOC01-appb-I000043
 
Figure JPOXMLDOC01-appb-I000043
 
  窒素雰囲気下、56 %水素化ナトリウム2.4 g、脱水N,N-ジメチルホルムアミド130 mlを加え、撹拌を行った。次に中間体Ｂ 15.4 g(0.046 mol)を脱水N,N-ジメチルホルムアミド154 mlに溶解させた溶液を30分かけて滴下した。その後、1時間撹拌を続けた。次に中間体Ｅ 22.0 g(0.042 mol) を脱水N,N-ジメチルホルムアミド220 mlに溶解させた溶液を30分かけて滴下した。その後、4時間撹拌を続けた。次に同フラスコ内に蒸留水500 gを加え、析出した黄色結晶をろ取した。ろ取した黄色結晶を、リスラリーを行い、乾燥した。その後、シリカゲルカラムにて精製を行い、化合物３－１５ 9.2 g(0.011 mol、収率27 %)を得た。
APCI-TOFMS, m/z 818 [M+H]+、1H -NMR測定結果（測定溶媒：THF-d8）を図２に示す。 Under a nitrogen atmosphere, 2.4 g of 56% sodium hydride and 130 ml of dehydrated N, N-dimethylformamide were added and stirred. Next, a solution prepared by dissolving 15.4 g (0.046 mol) of Intermediate B in 154 ml of dehydrated N, N-dimethylformamide was added dropwise over 30 minutes. Thereafter, stirring was continued for 1 hour. Next, a solution prepared by dissolving 22.0 g (0.042 mol) of the intermediate E in 220 ml of dehydrated N, N-dimethylformamide was added dropwise over 30 minutes. Thereafter, stirring was continued for 4 hours. Next, 500 g of distilled water was added to the flask, and the precipitated yellow crystals were collected by filtration. The yellow crystals collected by filtration were reslurried and dried. Thereafter, purification was performed on a silica gel column to obtain 9.2 g (0.011 mol, yield 27%) of compound 3-15.
APCI-TOFMS, m / z 818 [M + H] + , 1 H -NMR measurement results (measuring solvent: THF-d8) are shown in FIG.
  また、上記と同様にして、化合物１－３１、２－３、３－２２、５－１９、６－１１、６－１７及び６－３０を合成した。 In the same manner as described above, compounds 1-31, 2-3, 3-22, 5-19, 6-11, 6-17 and 6-30 were synthesized.
実施例１
  膜厚110 nmのITOからなる陽極が形成されたガラス基板上に、各薄膜を真空蒸着法にて、真空度4.0×10-5 Paで積層させた。まず、ITO上に銅フタロシアニン(CuPC)を25 nmの厚さに形成した。次に、正孔輸送層として4,4'-ビス[N-(1-ナフチル)-N-フェニルアミノ]ビフェニル（NPB）を40 nmの厚さに形成した。次に、正孔輸送層上に、ホスト材料としての合成例１で得た化合物３－１５と、燐光発光ドーパントとしてのトリス（2‐フェニルピリジン）イリジウム（III）（Ir(ppy)3）とを異なる蒸着源から、共蒸着し、40 nmの厚さに発光層を形成した。発光層中のIr(ppy)3の濃度は10.0 wt％であった。次に、電子輸送層としてトリス（８－ヒドロキシキノリナト）アルミニウム（III）（Alq3）を20 nmの厚さに形成した。更に、電子輸送層上に、電子注入層としてフッ化リチウム（LiF）を1.0 nmの厚さに形成した。最後に、電子注入層上に、電極としてアルミニウム（Al）を70 nmの厚さに形成し、有機ＥＬ素子を作製した。 Example 1
Each thin film was laminated at a vacuum degree of 4.0 × 10 −5 Pa by a vacuum deposition method on a glass substrate on which an anode made of ITO having a thickness of 110 nm was formed. First, copper phthalocyanine (CuPC) was formed to a thickness of 25 nm on ITO. Next, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) was formed to a thickness of 40 nm as a hole transport layer. Next, on the hole transport layer, compound 3-15 obtained in Synthesis Example 1 as a host material, tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3 ) as a phosphorescent dopant, and Were co-deposited from different deposition sources to form a light emitting layer with a thickness of 40 nm. The concentration of Ir (ppy) 3 in the light emitting layer was 10.0 wt%. Next, tris (8-hydroxyquinolinato) aluminum (III) (Alq3) was formed to a thickness of 20 nm as an electron transport layer. Further, on the electron transport layer, lithium fluoride (LiF) was formed to a thickness of 1.0 nm as an electron injection layer. Finally, on the electron injection layer, aluminum (Al) was formed as an electrode to a thickness of 70 nm to produce an organic EL element.
  得られた有機ＥＬ素子に外部電源を接続し直流電圧を印加したところ、表１のような発光特性を有することが確認された。表１において、輝度、電圧及び発光効率は、10mA/cm2での値を示す。また、輝度半減時間は、40 mA/cm2の一定電流駆動で評価し、この結果を初期輝度1000 cd/m2の場合に換算した値を示す。なお、素子発光スペクトルの極大波長は520 nmであり、Ir(ppy)3からの発光が得られていることがわかった。 When an external power source was connected to the obtained organic EL element and a DC voltage was applied, it was confirmed that the organic EL element had the light emission characteristics as shown in Table 1. In Table 1, the luminance, voltage, and luminous efficiency show values at 10 mA / cm 2 . Further, the luminance half time is evaluated by constant current drive of 40 mA / cm 2 , and the result is converted into a value when the initial luminance is 1000 cd / m 2 . The maximum wavelength of the device emission spectrum was 520 nm, and it was found that light emission from Ir (ppy) 3 was obtained.
実施例２
  発光層のホスト材料として、化合物１－３１を用いた以外は実施例１と同様にして有機ＥＬ素子を作製した。 Example 2
An organic EL device was produced in the same manner as in Example 1 except that Compound 1-31 was used as the host material for the light emitting layer.
実施例３
  発光層のホスト材料として、化合物２－３を用いた以外は実施例１と同様にして有機ＥＬ素子を作製した。 Example 3
An organic EL device was produced in the same manner as in Example 1 except that Compound 2-3 was used as the host material for the light emitting layer.
実施例４
  発光層のホスト材料として、化合物３－２２を用いた以外は実施例１と同様にして有機ＥＬ素子を作製した。 Example 4
An organic EL device was produced in the same manner as in Example 1 except that Compound 3-22 was used as the host material for the light emitting layer.
実施例５
  発光層のホスト材料として、化合物５－１９を用いた以外は実施例１と同様にして有機ＥＬ素子を作製した。 Example 5
An organic EL device was produced in the same manner as in Example 1 except that Compound 5-19 was used as the host material for the light emitting layer.
実施例６
  発光層のホスト材料として、化合物６－１１を用いた以外は実施例１と同様にして有機ＥＬ素子を作製した。 Example 6
An organic EL device was produced in the same manner as in Example 1 except that Compound 6-11 was used as the host material for the light emitting layer.
実施例７
  発光層のホスト材料として、化合物６－１７を用いた以外は実施例１と同様にして有機ＥＬ素子を作製した。 Example 7
An organic EL device was produced in the same manner as in Example 1 except that Compound 6-17 was used as the host material for the light emitting layer.
実施例８
  発光層のホスト材料として、化合物６－３０を用いた以外は実施例１と同様にして有機ＥＬ素子を作製した。 Example 8
An organic EL device was produced in the same manner as in Example 1 except that Compound 6-30 was used as the host material for the light emitting layer.
比較例１
  発光層のホスト材料として、下記化合物Ｈ－１を用いた以外は実施例１と同様にして有機ＥＬ素子を作製した。 Comparative Example 1
An organic EL device was produced in the same manner as in Example 1 except that the following compound H-1 was used as the host material for the light emitting layer.

Figure JPOXMLDOC01-appb-I000044
 
Figure JPOXMLDOC01-appb-I000044
 
　実施例２～８及び比較例１で得た有機ＥＬ素子の素子発光スペクトルの極大波長はいずれも520 nmであり、Ir(ppy)3からの発光が得られていることがわかった。発光特性ならびに寿命特性を表１に示す。 The maximum wavelengths of the device emission spectra of the organic EL devices obtained in Examples 2 to 8 and Comparative Example 1 were all 520 nm, indicating that light emission from Ir (ppy) 3 was obtained. The light emission characteristics and life characteristics are shown in Table 1.
Figure JPOXMLDOC01-appb-T000045
  
Figure JPOXMLDOC01-appb-T000045
  
  実施例１～８の有機ＥＬ素子は比較例１に対して初期特性ならびに寿命特性が向上しており、これより、一分子中に異なるインドロカルバゾール骨格を有する材料を発光層主成分に使用することで、有機ＥＬ素子特性が改善することが判る。 The organic EL elements of Examples 1 to 8 have improved initial characteristics and lifetime characteristics as compared with Comparative Example 1. From this, a material having a different indolocarbazole skeleton in one molecule is used as a main component of the light emitting layer. This shows that the characteristics of the organic EL element are improved.
産業上の利用の可能性Industrial applicability
  本発明の有機電界発光素子において使用されるインドロカルバゾール化合物は、一分子中に二種類以上のインドロカルバゾール異性体骨格を有するか、または同一異性体であっても分子構造が非対称となる結合様式を有することにより、正孔、電子移動速度の微調整、並びにＩＰ、ＥＡ、Ｔ１の各種エネルギー値の制御が可能となる。その結果、該インドロカルバゾール化合物を用いた有機ＥＬ素子において発光層中の最適なキャリアバランスを実現し、発効特性の大幅な改善が可能となる。さらに、このインドロカルバゾール化合物は酸化、還元、励起の各活性状態で安定性を向上させることが可能であり、同時に良好なアモルファス特性を有することから、駆動寿命が長く、耐久性の高い有機ＥＬ素子を実現できる。また、溶解性の向上等の機能を付与させた材料設計が可能であり、ウェットプロセスにより適した材料を与えることができる。
  本発明による有機ＥＬ素子は、発光特性、駆動寿命ならびに耐久性において、実用上満足できるレベルにあり、フラットパネルディスプレイ（携帯電話表示素子、車載表示素子、ＯＡコンピュータ表示素子やテレビ等）、面発光体としての特徴を生かした光源（照明、複写機の光源、液晶ディスプレイや計器類のバックライト光源）、表示板や標識灯等への応用において、その技術的価値は大きいものである。 The indolocarbazole compound used in the organic electroluminescence device of the present invention has two or more types of indolocarbazole isomer skeleton in one molecule, or a bond having an asymmetric molecular structure even in the same isomer. By having a mode, it becomes possible to finely adjust the hole and electron transfer speeds and to control various energy values of IP, EA, and T1. As a result, in the organic EL device using the indolocarbazole compound, the optimum carrier balance in the light emitting layer is realized, and the effect characteristics can be greatly improved. Furthermore, this indolocarbazole compound can improve stability in each active state of oxidation, reduction, and excitation, and at the same time has good amorphous characteristics, so it has a long driving life and high durability. An element can be realized. In addition, a material design provided with functions such as improvement in solubility is possible, and a material more suitable for a wet process can be provided.
The organic EL device according to the present invention has practically satisfactory levels in terms of light emission characteristics, driving life and durability, flat panel display (mobile phone display device, in-vehicle display device, OA computer display device, television, etc.), surface light emission, etc. Its technical value is great in applications to light sources (lighting, light sources for copying machines, backlight light sources for liquid crystal displays and instruments), display boards, and sign lamps that make use of the characteristics of the body.

Claims (4)

  1.   基板上に、陽極、燐光発光層を含む有機層及び陰極が積層されてなる有機電界発光素子において、燐光発光層、正孔輸送層、電子輸送層及び正孔阻止層からなる群れから選ばれる少なくとも一つの有機層中に、一般式（１）で表されるインドロカルバゾール化合物を含有することを特徴とする有機電界発光素子。
    Figure JPOXMLDOC01-appb-I000001
     
      一般式（１）中、Ｌは（ｍ＋ｎ＋ｐ＋ｑ）価の炭素数６～５０の芳香族炭化水素基又は炭素数３～５０の芳香族複素環基を表し、Ｙ1～Ｙ4はそれぞれ式（1a-1）～（1a-6）のいずれかで表される基であり、少なくとも1つは異なる基である。ｍは１～３の整数、ｎは１～３の整数、ｐは０～３の整数、ｑは０～３の整数を表し、ｍ＋ｎ＋ｐ＋ｑは２～６である。
    Figure JPOXMLDOC01-appb-I000002
     
      式（1a-1）～（1a-6）中、Ａは独立に炭素数１～１０のアルキル基、炭素数３～１１のシクロアルキル基、炭素数６～５０の芳香族炭化水素基又は炭素数３～５０の芳香族複素環基を示す。Ｒ1～Ｒ3はそれぞれ独立に、水素、炭素数１～１０のアルキル基、炭素数３～１１のシクロアルキル基、炭素数６～１２の芳香族炭化水素基又は炭素数３～１１の芳香族複素環基を示す。ただし、式（1a-1）、（1a-2）、（1a-4）及び（1a-6）において、Ｒ3はＲ3が結合する六員環と共に縮合環を形成しても良い。     In an organic electroluminescent device in which an anode, an organic layer including a phosphorescent light emitting layer and a cathode are laminated on a substrate, at least selected from the group consisting of a phosphorescent light emitting layer, a hole transport layer, an electron transport layer and a hole blocking layer An organic electroluminescent device comprising an indolocarbazole compound represented by the general formula (1) in one organic layer.
    Figure JPOXMLDOC01-appb-I000001

    In the general formula (1), L represents an (m + n + p + q) -valent aromatic hydrocarbon group having 6 to 50 carbon atoms or an aromatic heterocyclic group having 3 to 50 carbon atoms, and Y 1 to Y 4 are each represented by the formula (1a -1) to (1a-6), and at least one is a different group. m is an integer of 1 to 3, n is an integer of 1 to 3, p is an integer of 0 to 3, q is an integer of 0 to 3, and m + n + p + q is 2 to 6.
    Figure JPOXMLDOC01-appb-I000002

    In formulas (1a-1) to (1a-6), A is independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 11 carbon atoms, an aromatic hydrocarbon group having 6 to 50 carbon atoms, or carbon. An aromatic heterocyclic group having a number of 3 to 50 is shown. R 1 to R 3 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 11 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic group having 3 to 11 carbon atoms. Represents a heterocyclic group. However, the formula (1a-1), (1a -2), in (1a-4) and (1a-6), R 3 may form a condensed ring together with the six-membered ring to which R 3 binds.
  2.   一般式（１）で表されるインドロカルバゾール化合物が、一般式（２）～（７）のいずれかで表されるインドロカルバゾール化合物である請求項１に記載の有機電界発光素子。

    Figure JPOXMLDOC01-appb-I000003
     
      一般式（２）～（７）中、Ｌ、Ａ、Ｒ1～Ｒ3、ｍ及びｎは一般式（１）及び式（1a-1）～（1a-6）と同意である。     The organic electroluminescent device according to claim 1, wherein the indolocarbazole compound represented by the general formula (1) is an indolocarbazole compound represented by any one of the general formulas (2) to (7).

    Figure JPOXMLDOC01-appb-I000003

    In the general formulas (2) to (7), L, A, R 1 to R 3 , m and n are the same as the general formula (1) and the formulas (1a-1) to (1a-6).
  3.   一般式（２）～（７）で表されるインドロカルバゾール化合物において、ｍ及びｎがそれぞれ１である請求項２に記載の有機電界発光素子。 The organic electroluminescent device according to claim 2, wherein m and n are each 1 in the indolocarbazole compounds represented by the general formulas (2) to (7).
  4.   インドロカルバゾール化合物を含む有機層が、燐光発光ドーパントを含有する発光層であることを特徴とする請求項１～３のいずれかに記載の有機電界発光素子。 4. The organic electroluminescent device according to claim 1, wherein the organic layer containing an indolocarbazole compound is a light emitting layer containing a phosphorescent dopant.
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JP5596706B2 (en) 2014-09-24
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JPWO2011080972A1 (en) 2013-05-09
KR101758865B1 (en) 2017-07-17

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